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WO2008052962A1 - Procédé de coloration de substrats de polypropylène - Google Patents

Procédé de coloration de substrats de polypropylène Download PDF

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Publication number
WO2008052962A1
WO2008052962A1 PCT/EP2007/061608 EP2007061608W WO2008052962A1 WO 2008052962 A1 WO2008052962 A1 WO 2008052962A1 EP 2007061608 W EP2007061608 W EP 2007061608W WO 2008052962 A1 WO2008052962 A1 WO 2008052962A1
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WIPO (PCT)
Prior art keywords
substrate
process according
polypropylene
melamine
aqueous
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Application number
PCT/EP2007/061608
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German (de)
English (en)
Inventor
Salvador Roig Ramis
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BASF SE
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BASF SE
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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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • 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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • D06P5/04—After-treatment with organic compounds
    • D06P5/06—After-treatment with organic compounds containing nitrogen
    • 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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • D06P5/04—After-treatment with organic compounds
    • D06P5/08—After-treatment with organic compounds macromolecular
    • 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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/22—Effecting variation of dye affinity on textile material by chemical means that react with the fibre
    • 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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/30—Ink jet printing
    • 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
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5285—Polyurethanes; Polyurea; Polyguanides
    • 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
    • D06P1/56—Condensation products or precondensation products prepared with aldehydes
    • 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 process for coloring a substrate from polypropylene, which comprises
  • the present invention finally relates to substrates obtainable by the process of the present invention.
  • Goals include distinctly crisper contours (improved definition) for the prints on the substrate in order that higher resolutions (higher dpi) may be achieved for the prints. Goals further include high in-service fastnesses, for example washfastness and rubfastness.
  • EP-A 0 928 841 describes the use of natural thickeners and of bivalent metal salts to print direct dyes and pigments onto silk.
  • the use of bivalent metal salts is not desirable in several cases.
  • WO 2004/031473 discloses pretreating textiles with a pretreatment liquor comprising at least one polycationic compound and at least one thickener.
  • the textiles obtained exhibit improved ink holdout when printed.
  • Fabric hand of printed textiles thus obtainable, although not adversely affected, could do with improvement in many cases.
  • the rub- fastness of printings with inks based on pigments are, however, in need of improvement.
  • WO 2006/000384 suggests to pretreat textile substrates with a liquor containing a thickener and a resin selected from melamine derivatives, dimethyloldihydroxyethyle- neurea (DMDHEU) and derivatives of DMDHEU and then print onto said substrates with the ink-jet method.
  • a liquor containing a thickener and a resin selected from melamine derivatives, dimethyloldihydroxyethyle- neurea (DMDHEU) and derivatives of DMDHEU and then print onto said substrates with the ink-jet method.
  • DMDHEU dimethyloldihydroxyethyle- neurea
  • the present invention therefore had for its object to provide a process which avoids the disadvantages mentioned at the beginning and especially provides substrates from polypropylene which, after printing, show improved properties such as rub fastness after repeated bending or folding.
  • inks shall exhibit good holdout on print- ing.
  • the present invention further had for its object to provide printed substrates from polypropylene which avoid the
  • substrates from polypropylene which may take any form.
  • substrates from polypropylene are flexible which means that they can be repeatedly bent or folded manually without deterioration of mechanical properties, for example films and foils, preferably textile substrates such as fibers, mi- crofibers, yarns, threads, knits, wovens, nonwovens and garments composed of polypropylene or mixtures comprising polypropylene.
  • textile substrates are initially treated in step (A) with an aqueous pretreatment liquor comprising
  • Examples of useful resins (a) are dimethyloldihydroxyethyleneurea (DMDHEU)
  • DMDHEU for example etherification products of DMDHEU with for example Ci-C4-alkanol, especially with methanol and with ethanol.
  • Further useful de- rivatives of DMDHEU are bridged derivatives disclosed in EP 0 923 560, and mixedly alkylated or hydroxyalkoxyalkylated bis-4,5-dihydroxyimidazolidin-2-ones as described in WO 98/29393.
  • Preference is given to choosing resins (a) from melamine derivatives which may be singly to sixtuply condensed with one or more aldehydes and etherified with at least one aliphatic alcohol.
  • At least one aldehyde is selected from C6-Ci4-arylaldehydes, for example 2-naphthaldehyde, 1-naphthaldehyde and especially benzaldehyde,
  • Ci-Cio-alkylaldehydes wherein Ci-Cio-alkyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1 ,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n- octyl, n-nonyl, n-decyl; more preferably Ci-C4-alkyl such as methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
  • Useful aliphatic alcohols include Ci-Cio-alkanols, especially primary Ci-Cio-alkanols and most preferably methanol and ethanol.
  • Useful aliphatic alcohols further include polyhydric alcohols such as for example ethylene glycol, propylene glycol, butylene glycol, pentane-1 ,2-diol, hexane-1 ,2-diol, 1 ,3-propanediol, 1 ,4-butanediol, 1 ,6- hexanediol, 1 ,12-dodecanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, glycerol, diglycerol, triglycerol, polyethylene glycol having on average from 5 to 50 ethylene oxide units per molecule (number average), polypropylene glyco
  • Resin (a) is preferably a melamine derivative, for example a melamine derivative of the general formula IV
  • R 1 to R 6 are the same or different and are each defined as follows: hydrogen or
  • z is in the range from 1 to 10 and may but need not be an integer
  • R 7 is in each occurrence the same or different and selected from
  • Ci-Ci2-alkyl branched or unbranched, selected from Ci-Ci2-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec- pentyl, neopentyl, 1 ,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, n-nonyl, n-decyl and n-dodecyl; preferably Ci-C ⁇ -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-buty
  • alkoxyalkylene such as for example (-CH 2 -CH 2 -O)m-H, (-CHCH 3 -CH 2 -O)m-H,
  • R 8 is in each occurrence different or preferably the same and selected from
  • Ci-Ci2-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1 ,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, n-nonyl, n-decyl and n-dodecyl; preferably Ci-C ⁇ -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-
  • the R 1 , R 3 and R 5 radicals are preferably different.
  • R 1 and R 2 it is more preferable for R 1 and R 2 to be hydrogen and more preferable for R 3 and R 4 each to be CH 2 -OH. It is most preferable for R 1 and R 2 each to be hydrogen and for R 3 to be CH 2 -OH.
  • Many melamine derivatives of the general formula I are known per se and are commercially available, for example as Luwipal® from BASF Aktiengesellschaft and as Cymel® 327 from Cytec. Melamine derivatives for the purposes of the present invention are generally not pure in the sense of having one defined formula; typically, one observes intermolecular rearrangements of the R 1 to R 6 radicals, i.e., transacetalization reactions and transaminalization reactions, and also to a certain degree condensation reactions and elimination reactions.
  • the formula V indicated above is to be understood as defining the stoichiometric ratios of the substituents and as comprising intermolecular rearrangement products and condensation products as well.
  • the melamine derivatives which are most preferably used as resin (a) are obtainable by reaction of melamine with one to three, preferably with 1.4 to 2.8 and more preferably with 1.5 to 2.6 equivalents of at least one aliphatic aldehyde, for example propion- aldehyde, acetaldehyde and especially formaldehyde. This reaction is followed by an etherification with 4.5 to 15 equivalents, preferably up to 10 and more preferably up to 6 equivalents of at least one di- or more highly hydric aliphatic alcohol.
  • Melamine derivatives used as resin (a) in the present invention can be prepared in a conventional manner.
  • Melamine derivatives which are particularly preferred for use as resin (a) can be prepared by initially reacting melamine with one to three equivalents of at least one aliphatic aldehyde and then etherifying the reaction product with 4.5 to 10 equivalents of at least one polyhydric aliphatic alcohol.
  • the reaction of melamine with at least one aliphatic aldehyde in one embodiment of the present invention is carried out in aqueous formulation, preferably at pH values in the range from 7 to 10 and more preferably at pH values in the range from 8 to 9.
  • aqueous formulation preferably at pH values in the range from 7 to 10 and more preferably at pH values in the range from 8 to 9.
  • no water is used and melamine and at least one aldehyde, especially melamine and paraformaldehyde, are mixed and the two reactants are made to react with each other.
  • reaction of melamine with at least one aliphatic aldehyde is carried out at temperatures in the range from 50 to 105 0 C and preferably in the range from 70 to 90 0 C.
  • reaction of melamine with at least one aliphatic aldehyde is carried out at atmospheric pressure.
  • reac- tion of melamine with at least one aliphatic aldehyde is carried out at pressures in the range from 1.01 to 50 bar and preferably up to 10 bar.
  • reaction of melamine with at least one aliphatic aldehyde is carried out in the presence of at least one catalyst, examples being sodium hydroxide and potassium hydroxide.
  • the etherification with at least one polyhydric aliphatic alcohol is carried out in aqueous phase at pH values in the range from 1 to 6 and preferably in the range from 5 to 5.5. Desired pH values can be set by addition of an acid such as for example trifluoroacetic acid, methylsulfonic acid, para-toluenesulfonic acid, benzenesulfonic acid, sulfuric acid, phosphoric acid or nitric acid.
  • an acid such as for example trifluoroacetic acid, methylsulfonic acid, para-toluenesulfonic acid, benzenesulfonic acid, sulfuric acid, phosphoric acid or nitric acid.
  • the etherification with at least one polyhydric aliphatic alcohol is carried out at temperatures in the range from 20 to 100 0 C and preferably in the range from 30 to 70 0 C.
  • the etherification with at least one polyhydric aliphatic alcohol is carried out at atmospheric pressure.
  • the eth- erification with at least one polyhydric aliphatic alcohol is carried out at pressures in the range from 1.01 to 50 bar.
  • excess aliphatic aldehyde can be distilled off. It is also possible not to distill off excess aliphatic aldehyde and for excess aliphatic alde- hyde to be removed from the reaction equilibrium by means of suitable reagents, for example oxidizing agents such as nitric acid for example.
  • suitable reagents for example oxidizing agents such as nitric acid for example.
  • the melamine derivatives preferred for use as resin (a) are prepared by omitting distillations between the reaction of melamine with at least one aldehyde and the etherification with at least one polyhydric aliphatic alcohol.
  • melamine derivatives preferred for use as resin (a) are isolated, for example by evaporating any solvents used such as water in particular. Spray drying is a particularly suitable method of isolating melamine deriva- tives used as resin (a) in the present invention.
  • melamine derivatives preferred for use as resin (a) are not isolated but used in the form of dispersions, preferably in the form of aqueous dispersions.
  • aqueous pretreatment liquors further comprise at least one thickener (b).
  • useful thickeners (b) include natural thickeners such as alginates, polysaccharides, starch, carboxymethylcellulose, guar gum powder and also derivatives thereof, and synthetic thickeners such as if appropriate acrylic acid homo- and copolymers, which may be crosslinked, for example by interpolymerization of at least one compound of the general formula
  • R 9 is methyl or preferably hydrogen.
  • Preferred thickeners (b) are associative thickeners of the general formula I, Il and/or III
  • E is in each occurrence the same or different and selected from -CH2-CH2-, -CH 2 -CH(CH 3 )-, -CH 2 -CH(C 2 H 5 )-,
  • y is an integer from 1 to 100,000 and preferably in the range from 10 to 10,000
  • T is in each occurrence the same or different and a diisocyanate-derived unit
  • x is an integer from 1 to 500, preferably in the range from 1 to 2 and more preferably about 1 ,
  • U is in each occurrence the same or different and selected from units derived from aliphatic or aromatic alcohols, thiols, amines or carboxylic acids each having 4 or more carbon atoms and preferably not less than 6 carbon atoms, aromatic alcohols, thiols, amines or carboxylic acids each having 6 or more carbon atoms, al- cohols, thiols, amines or carboxylic acids having C7-Ci3-aralkyl moieties or het- eroaromatic alcohols, thiols, amines or carboxylic acids.
  • Associative thickeners of the general formula I are obtainable by reaction of (i) at least one polyetherdiol with
  • R 10 R 11 NH or R 10 -COOH, where R 10 and R 11 may be the same or different and are each selected from aliphatic radicals having not less than 4 carbon atoms, aromatic radicals having not less than 6 carbons and heteroaromatic radicals and where R 10 -OH may be alkoxylated, and also further derivatives of these com- pounds that are capable of forming a urethane, thiourethane or urea bond.
  • Preferred polyetherdiols (i) for the purposes of the present invention are polyethylene glycol, polypropylene glycol and polytetrahydrofuran, but also copolymers of ethylene oxide and propylene oxide or butylene oxide or terpolymers of ethylene oxide, propyl- ene oxide and butylene oxide, which copolymers may take the form of block copolymers or random copolymers or terpolymers.
  • Useful diisocyanates (ii) include diisocyanates having NCO groups of the same or a different reactivity.
  • diisocyanates having NCO groups of the same reactiv- ity are aromatic or aliphatic diisocyanates, preference being given to aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), oc- tamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetramethyl- hexane diisocyanate, 1 ,4-, 1 ,3- or 1 ,2-diisocyanatocyclohexane, 4,4'-diisocyanatocyclohexylmethane, 1 -isocyanato-S ⁇ -trimethyl- ⁇ -isocyanato-
  • Preferred diisocyanates having NCO groups of differing reactivity are the readily and inexpensively available isocyanates such as for example 2,4-tolylene diisocyanate (2,4-TDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), triisocyanatotoluene as representatives of aromatic diisocyanates or aliphatic diisocyanates, such as 2-butyl- 2-ethylpentamethylene diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,4'-methylenebis(cyclohexyl) diisocyanate and 4-methylcyclohexane 1 ,3-diisocyanate (H-TDI).
  • isocyanates such as for example 2,4-tolylene diisocyanate (2,4-TDI), 2,4'-diphenylmethane di
  • isocyanates having groups differing in reactivity are 1 ,3-phenylene diisocyanate, 1 ,4-phenylene diisocyanate, 1 ,5-naphthylene diisocyanate, diphenyl diisocyanate, toluidine diisocyanate and 2,6-tolylene diisocyanate. It is naturally also possible to use mixtures of two or more of the aforementioned isocy- anates for synthesis.
  • Polyisocyanates can be used to a certain extent alongside diisocyanates, for example in amounts of up to 10% by weight based on the total amount of di- and polyisocy- anate.
  • useful polyisocyanates are biurets and allophanates of HDI or TDI.
  • Very particularly preferred diisocyanates (ii) are HDI, IPDI, MDI and TDI.
  • the molar ratio of polyetherdiols (i) to diisocyanates (ii) is generally in the range from 0.3:1 to 1 :1 and preferably about 0.5:1.
  • reaction of diisocyanate (ii) with polyetherdiol (i) is typically carried out in the presence of one or more catalysts.
  • the catalyst or catalysts are preferably used in an amount from 0.01 % to 10% by weight and preferably from 0.05% to 5% by weight, based on diisocyanate (ii).
  • Useful catalysts to speed especially the reaction between the NCO groups of diisocy- anate (ii) and the hydroxyl groups of polyetherdiol (i) are well-known tertiary amines, for example triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'- dimethylpiperazine, 2-dimethylaminoethoxyethanol, 1 ,4-diazabicyclo[2.2.2]octane (DABCO) and the like and also in particular organic metal compounds such as titanate esters, iron(lll) acetylacetonate, tin compounds, for example tin diacetate, tin dioc- tanoate, tin dilaurate or the dialkyl derivatives of tin dialkyl salts of aliphatic carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate or the like.
  • the synthesis of the associative thickeners (b) is generally carried out without a solvent or in an aprotic solvent, with a suitable solution being in principle any solution which reacts neither with polyurethane nor with polyetherdiol (i) nor with diisocyanate (ii), for example tetrahydrofuran, diethyl ether, diisopropyl ether, chloroform, dichloromethane, di-n-butyl ether, acetone, N-methylpyrrolidone (NMP), xylene, toluene, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK) or 1 ,4-dioxane.
  • Preferred reaction temperatures are in the range from -20 0 C to the boiling point of the solvent used.
  • the reac- tion is generally carried out under atmospheric pressure, but it may also be carried out in autoclaves at up to 20 bar.
  • Reacting NCO-terminated products of polyetherdiol (i) with diisocyanate (ii) with aliphatic or aromatic alcohols, thiols, primary or secondary amines or carboxylic acids (iii) converts the reaction products of the components (i) and (ii), which comprise free iso- cyanate groups, into hydrophobicized products.
  • Suitable are in particular alcohols R 10 -OH and primary or secondary amines R 10 -NH2 and R 10 R 11 NH, in each of which R 10 and R 11 may be the same or different and are each selected from
  • C4-C6o-alkyl such as for example n-butyl, isobutyl, n-pentyl, preferably C6-C4o-alkyl such as for example n-hexyl and n-heptyl and especially C8-C4o-alkyl such as for example n- octyl, n-nonyl, n-decyl, n-dodecyl, n-hexadecyl or n-eicosyl;
  • C6-Ci4-aryl such as phenyl, ⁇ -naphthyl, ⁇ -naphthyl, 1-anthracenyl, 2-anthracenyl or 9- anthracenyl
  • heteroaromatic radicals such as ⁇ -pyridyl, ⁇ -pyridyl, ⁇ -pyridyl, N-pyrryl, ⁇ -pyrryl, ⁇ - pyrryl, porphyrinyl, 2-furanyl, 3-furanyl, 2-thiophenyl, 3-thiophenyl, N-pyrazolyl, N- imidazolyl, N-triazolyl, N-oxazolyl, N-indolyl, N-carbazolyl, 2-benzofuranyl, 2- benzothiophenyl, N-indazolyl, benzotriazolyl, 2-quinolinyl, 3-isoquinolinyl and ⁇ - phenanthrolinyl;
  • C7-Ci3-aralkyl preferably C7- to Ci2-phenylalkyl such as benzyl, 1-phenethyl, 2- phenethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, neophyl (1-methyl-1- phenylethyl), 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and 4-phenylbutyl, more preferably benzyl.
  • Ci2-phenylalkyl such as benzyl, 1-phenethyl, 2- phenethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, neophyl (1-methyl-1- phenylethyl), 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and 4-phenylbutyl, more preferably benzyl.
  • Alcohols R 10 -OH may also have been alkoxylated with one or more equivalents of ethylene oxide, propylene oxide or butylene oxide, in which case not only homo- but also (block) copolymers of the identified alkylene oxides can be used, typically having about 20 to 500 alkylene oxide units. Alcohols R 10 -OH may further be alkoxylated with THF.
  • the compound of the general formula R 10 -OH, R 10 -SH, R 10 -NH 2 , R 10 R 11 NH or R 10 -COOH (iii) is used with regard to the free isocyanate groups in an at least stoichiometric amount, but frequently in stoichiometric excess, for example from 50 to 100 mol%, based on free NCO groups.
  • Hydrophobic groups R 10 may also be attached to polyetherdiol (i) via an ester or ether bridge.
  • Associative thickeners of the general formula Il are thus obtainable for example by reaction of
  • Associative thickeners of the formula III are obtained for example from diisocyanate (ii) and at least one compound of the general formula R 10 -OH, R 10 -SH, R 10 -NH 2 , R 10 R 11 NH or R 10 -COOH (iii) without polyetherdiols (i) being present.
  • the compound of the general formula R 10 -OH, R 10 -SH, R 10 -NH 2 , R 10 R 11 NH or R 10 -COOH (iii) or to be more precise the compounds (iii) may be used in stoichiometric excess, based on diisocyanate (ii).
  • substrates from polypropylene are first treated with at least one aqueous pretreatment liquor comprising the above-described components (a) and (b).
  • aqueous pretreatment liquor comprising the above-described components (a) and (b)
  • the substrate from polypropylene is contacted at least once with aqueous pretreatment liquor and subjected to the action thereof for a certain period, for example for a period in the range from 0.1 second to 2 hours, and is subsequently removed as pretreated substrate.
  • Contacting can be effected in various ways. It is possible for example to apply inventive aqueous pretreatment liquor to textile substrate, for example by exhaust processes or batch or continuous processes involving forced application.
  • the textile substrate can be in a wound-up state and aqueous pretreatment liquor forced under pressure through the wound-up textile substrate, in which case the aqueous pretreatment liquor can flow from in to out or else, in fully flooded machines, from out to in.
  • aqueous pretreatment liquor can flow from in to out or else, in fully flooded machines, from out to in.
  • substrate from polypropylene is present in an unconstrained state in the aqueous pretreatment liquor and moves therewith.
  • substrate from polypropylene can be pulled through a standing bath comprising an aqueous pretreatment liquor.
  • substrate from polypro- pylene is repeatedly pulled through an aqueous pretreatment liquor and the direction of movement of the substrate from polypropylene should reverse.
  • This is useful for uniform application. More particular details concerning these application processes can be found in the relevant literature, for example Veredlung von Textilien, VEB subuch- verlag für, 1 st edition 1976, pages 93 ff.
  • Useful continuous processes for application include all processes whereby the aqueous pretreatment composition can be applied uniformly or imagewise. Of particular suitability here are all printing processes and also all processes in which the substrate from polypropylene is uniformly drenched with an aqueous pretreatment liquor. The difference to exhaust processes is that a forced application is realized. The aqueous pretreatment liquor need not have any affinity for fiber for these processes.
  • Useful printing processes for the application of an aqueous pretreatment liquor include for example all screen printing processes. Screen printing processes are important processes which are known in principle and are utilized inter alia in the production of printed fabrics. In screen printing, the aqueous pretreatment liquor is forced by a squeegee through a fine mesh and onto a substrate from polypropylene to be pre- treated. The mesh can be formed from synthetic fibers, as in flat screen printing machines, or metals, as in rotary screen printing machines.
  • Relief printing, gravure printing or roller printing being common printing processes, are also useful for applying inventive aqueous pretreatment liquor. Details concerning individual printing processes can be found on pages 1 10 ff. of the literature reference cited above.
  • any technique wherein any substrate from polypropylene is uniformly drenched with an aqueous pretreatment liquor can be accomplished for example using pad-mangle technology wherein substrate from polypropylene is led through a trough filled with aqueous pretreatment liquor and subsequently squeezed off by two rolls to a defined wet pickup. It is also possible to lead substrate from polypropylene through a nip formed between two rotat- ing rollers and filled with aqueous pretreatment liquor. The rollers lead to an intensive contacting of substrate from polypropylene with aqueous pretreatment liquor while at the same time squeezing off the substrate from polypropylene to the desired wet pickup. There are in addition many other possible configurations for this pad-mangle technology, which are all likewise useful for applying an aqueous pretreatment liquor.
  • aqueous pretreatment liquor can be applied by well-known spraying and pouring techniques.
  • substrate from polypropylene is contacted with sufficient pretreatment liquor to apply from 0.1 to 30 g of solids/m 2 of substrate from polypropylene, preferably from 1 g/m 2 to 25 g/m 2 and more preferably up to 15 g/m 2 .
  • the temperature chosen for the pretreat- ment liquor is in the range from 20 0 C to 60 0 C.
  • the rolls may be set to a nip pressure in the range from 2 to 3 bar for example.
  • aqueous pretreatment liquors comprise (a) from 0.1 % to 20%, preferably from 0.1 % to 15% by weight and more preferably from 0.1 % to 10% by weight of at least one resin selected from melamine deriva- tives, dimethyloldihydroxyethyleneurea (DMDHEU) and derivatives of DMDHEU,
  • the solids content of pretreatment liquors may be for example in the range from 10 g/l to 600 g/l and preferably in the range from 50 g/l to 500 g/l.
  • the contacting of substrate from polypro- pylene with aqueous pretreatment liquor may be followed by drying, for example to a residual moisture content in the range from 5% to 30% by weight.
  • one or more salts of mono- or bivalent metals or ammonium salts may be added to pretreatment liquor.
  • useful salts are ZnCb, Zn(NOs)2, each in its hydrated or nonhydrated form, NH 4 CI, (NH 4 ⁇ SO 4 , NaBF 4 , AlCh- ⁇ H2O, ammonium dihydrogen phosphate, diammonium hydrogen phos- phate, and most preferably MgCb, for example in the form of its hexahydrate.
  • inventive pretreatment liquors comprise one or more salts of mono- or bivalent metals or ammonium salts
  • the amounts will typically be in the range from 0.1 % to 30% by weight, based on resin (a), preferably in the range from 0.5% to 10% and more preferably in the range up to 8% by weight.
  • Step (B) of the process according to the present invention comprises printing pre- treated and if appropriate dried substrate from polypropylene, preferably by the ink jet process.
  • the ink jet process utilizes inks, which may be solvent or preferably water borne, that are sprayed as small droplets directly onto the substrate from polypropylene.
  • inks which may be solvent or preferably water borne
  • the ink jet inks used for printing substrates from polypropylene in the process of the present invention typically comprise water or water-solvent mixture and also finely divided organic or inorganic colorants which are preferably substantially insoluble in water or in the water-solvent mixture, examples being pigments as defined in German standard specification DIN 55944.
  • Disperse dyes can be used instead of pigments.
  • ink jet inks can also comprise direct dyes, acid dyes, reactive dyes or vat dyes as dissolved dyes.
  • the soluble dyes mentioned can be present as brightening agents in pigment-based ink jet inks, in which case soluble dyes (especially direct, acid or reactive dyes) which are similar in hue to the pigment are used.
  • Step (B) is particularly preferably carried out using at least one pigment-based ink jet ink which, as well as at least one pigment and water, comprises at least one dispers- ant.
  • Useful dispersants include for example those based on maleic acid-acrylic acid copolymers, especially those having an M n molecular weight in the range from 2 000 to 10 000 g/mol, which are useful in the form of random copolymers or block copolymers.
  • Useful dispersants further include N-vinylpyrrolidone homopolymers and acrylate-N- vinylpyrrolidine copolymers, especially N-vinylpyrrolidone homopolymers and acrylate- N-vinylpyrrolidine copolymers having an M n molecular weight in the range from 2,000 to 10,000 g/mol, in the form of random copolymers or block copolymers.
  • Useful dispersants also include those based on naphthalenesulfonic acid-formaldehyde condensates, for example according to US 5,186,846, or based on alkoxylated styry- lated and optionally sulfated alkylphenols or bisphenols for example according to US 4,218,218.
  • Useful dispersants further include random polyurethane copolymers as disclosed for example in WO 2004/31255 page 3 ff.
  • Ink Jet inks used in step (B) preferably comprise at least one solvent having a boiling point above 110 0 C, examples being ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, glycerol, diglycerol, propylene glycol, dipropylene glycol, room temperature liquid polytetrahydrofuran, 1 ,3-propanediol, mono-, di- or triethylene glycol mono-Ci-C4-alkyl esters in each of which Ci-C4-alkyl is selected from methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.
  • ink jet inks used in step (B) have a dynamic viscosity in the range from 1 to 30 mPa-s, preferably in the range from 1 to 20 mPa-s and more preferably in the range from 2 to 15 mPa-s, in each case determined at 20 0 C.
  • ink jet inks used in step (B) have a surface tension in the range from 20 to 70 mN/m, especially in the range from 20 to 40 mN/m and more preferably in the range from 25 to 35 mN/m, all determined at 20 0 C.
  • the pH of ink jet inks used in step (B) is generally in the range from 5 to 10 and preferably in the range from 7 to 9.
  • Ink jet inks used in step (B) may comprise further auxiliaries of the kind customary especially for aqueous ink jet inks and in the printing and coatings industry.
  • auxiliaries include erythritol, pentaerythritol, pentitols such as arabitol, adonitol and xylitol and hexitols such as sorbitol, mannitol and dulcitol.
  • Further examples are polyethylene glycols having an M w in the range from more than 2,000 g/mol to about 10,000 g/mol and preferably up to 8,000 g/mol.
  • preservatives such as for example 1 ,2-benzisothiazolin-3-one and its alkali metal salts, degas- sers/defoamers such as for example ethoxylated acetylenediols, which typically comprise from 20 to 40 mol of ethylene oxide per mole of acetylenediol and may also have a dispersing effect, viscosity regulators, flow agents, wetters (examples being wetting surfactants based on ethoxylated or propoxylated fatty or oxo alcohols, propylene ox- ide-ethylene oxide block copolymers, ethoxylates of oleic acid or alkylphenols, alkyl- phenol ether sulfates, alkylpolyglycosides, alkylphosphonates, alkylphenylphospho- nates, alkyl phosphates, alkylphenyl phosphates, or preferably
  • Inks used in step (B) may comprise one or more resins (a) in amounts of up to 10% by weight.
  • step (B) After having performed step (B), a substrate from propylene is obtained which is briefly referred to as printed substrate in the context of the present invention.
  • step (C) of the process of the present invention printed substrate is aftertreated with an aqueous formulation comprising at least one binder.
  • Binders in the context of the present invention are film-forming (co)polymers or pre- polymers.
  • binders are selected from acry- late binders and polyurethane binders.
  • binders are selected from film-forming (co)polymers which have a glass transition temperature above -50 0 C, preferably from -25°C up to 150 0 C and even more preferably up to +30 0 C. Glass transition temperatures can be calculated according to the Fox equation or be determined experimentally with methods known as such, e.g., DSC (Differential Scanning Calorimetry).
  • Acrylate binders in the context of the present invention can be selected from copolymers of at least one ethylenically unsaturated acid such as maleic acid, fumaric acid, E- and Z- crotonic acid, itaconic acid and particularly (meth)acrylic acid with at least one comonomer selected from monovinylaromatic compounds, Ci-Cio-alkyl esters of monoethylenically unsaturated carboxylic acids, monoethylenically unsaturated carboxamides, polyfunctional derivatives of ethylenically unsaturated carboxylic acids, and preferably at least one additional comonomer having at least one epoxy group, NH-CH2OH group or acetoacetyl group per molecule.
  • monovinylaromatic compounds examples include -methylstyrene, para-methylstyrene, 2,4-dimethylstyrene and especially styrene.
  • Ci-Cio-alkyl esters of monoethylenically unsaturated carboxylic acids are esters of branched or unbranched Ci-Cio-alkanol with one of the aforementioned monoethylenically unsaturated carboxylic acids.
  • Specific examples are: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate.
  • Particularly suitable monoethylenically unsaturated carboxamides are N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide,
  • Particularly suitable polyfunctional derivatives of ethylenically unsaturated carboxylic acids are compounds of the general formula Vl
  • X 1 and X 2 are the same or different and selected from oxygen, NH and N-R 11 ,
  • A is a spacer, for example branched or unbranched C2-C2o-alkylene or phenylene.
  • C 2 -C 2 o-alkylene examples include -(CH 2 ) 2 -, -CH 2 -CH(CH 3 )-, -(CH 2 ) 3 -, -CH 2 -CH(C 2 H 5 )-, -(CH 2 ) 4 -, -(CH 2 ) 5 -, -(CH 2 ) 6 -, -(CH 2 ) 7 -, -(CH 2 ) 8 -, -(CH 2 ) 9 -, -(CH 2 )io-; preferably C 2 -C 4 -alkylene; especially -(CH 2 ) 2 -, -CH 2 -CH(CH 3 )-, -(CH 2 ) 3 -, -(CH 2 ) 4 - and -CH 2 -CH(C 2 H 5 )-.
  • R 12 and R 13 are the same or different and selected from Ci-Cio-alkyl, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neopentyl, 1 ,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, more preferably unbranched Ci-C 4 -alkyl such as methyl, ethyl, n-propyl and n-butyl.
  • Ci-Cio-alkyl for example methyl, ethyl,
  • Particularly suitable comonomers having epoxy groups are for example glycidyl esters of maleic acid, fumaric acid, E- and Z- crotonic acid and especially of acrylic acid and of methacrylic acid.
  • Particularly suitable comonomers having NH-CH 2 OH groups are for example reaction products of formaldehyde with monoethylenically unsaturated carboxamides, especially N-methylolacrylamide and N-methylolmethacrylamide.
  • Particularly suitable comonomers having acetoacetyl groups are for example (meth)acrylates of alcohols of the general formula VII
  • R 14 is selected from branched or unbranched Ci-Cio-alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neopentyl, 1 ,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, more preferably unbranched Ci-C4-alkyl such as methyl, ethyl, n-propyl and n-butyl.
  • Ci-Cio-alkyl such as methyl, ethyl, n-
  • Film forming (co)polymers can be manufactured in a conventional manner, for example by emulsion polymerization with one or more free-radical starters in the presence of one or more emulsifiers. Particular preference is given to preparing film forming (co)polymers by an emulsion polymerization in seeded mode; that is, initially one or more water-insoluble polymers such as for example polystyrene are added in very small particles, for example having an average diameter in the range from 15 to 30 nm, which then promote droplet formation during the copolymerization.
  • One embodiment of the present invention comprises film forming (co)polymer having a dynamic viscosity in the range from 10 to 200 mPa-s, determined by the Brookfield method for example, at room temperature.
  • One embodiment of the present invention comprises film forming (co)polymer having in an amount from 0.1 % to 7% by weight of the total amount of binder.
  • polyurethane binders are polyurethanes, preferably hydroxyl terminated polyurethanes, made from at least one aliphatic or aromatic or cycloaliphatic di- or polyisocyanate or a mixture thereof, and at least one diol selected from hydroxyl-terminated polyesters or diols or polyols.
  • Suitable di- and polyiocyanates are 2,4- and 2,6-toluylene diisocyanate and mixtures of the foregoing (TDI), tetramethylenediisocyanate, hexamethylenediisocyanate (HDI), dodecamethylenediisocyanate, 1 ,4-cyclohexane-diisocyanate, 4,4'- dicyclohexylmethylene diisocyanate (MDI), isophorone diisocyanate (IPDI) and and mixtures thereof.
  • TDI 2,4- and 2,6-toluylene diisocyanate and mixtures of the foregoing
  • HDI hexamethylenediisocyanate
  • MDI 4,4'- dicyclohexylmethylene diisocyanate
  • IPDI isophorone diisocyanate
  • Preferred hydroxyl-terminated polyesters are made from at least one aliphatic or ali- cyclic (cycloaliphatic) diol, such as ethylene glycol, neopentylglycol (2,2- dimethylpropane 1 ,3-diol), dimethylol-1 ,4-cyclohexane, 1 ,4-butanediol, 1 ,6-hexanediol, 1 ,12-dodecanediol.
  • aliphatic or ali- cyclic (cycloaliphatic) diol such as ethylene glycol, neopentylglycol (2,2- dimethylpropane 1 ,3-diol), dimethylol-1 ,4-cyclohexane, 1 ,4-butanediol, 1 ,6-hexanediol, 1 ,12-dodecanediol.
  • Preferred polyurethane binders can bear an acid group such as a carboxyl group or a sulfonate group.
  • Acid group bearing polyurethanes can be made by, e.g., by carrying out the synthesis of the respective polyurethane in the presence of a diol or a diamine with primary or secondary amino groups and with a free carboxyl group or sulfonate group.
  • Suitable examples are 3,3-dimethylolpropanoic acid and 2-(2-aminoethyl) amino ethanesulfonic acid monoalkalimetall salt, in particular the respective sodium salt (see below).
  • aqueous formulation employed in step (C) also contains at least one fixing agent.
  • the aftertreatment step can be performed by additionally using a fixing agent, in the context of the present invention also referred to as fixing agent (e).
  • Suitable fixing agents can be selected from di- or polyisocyanates such as hexame- thylene diisocyanate. Di- and polyisocyanates are preferred fixing agents when using a polyurethane binder in step (C).
  • Suitable fixing agents (e) can further be selected from
  • melamine derivatives (e1) are optionally alkoxylated or alkoxyalkylated compounds or hemiaminalized melamines especially of the general formula VIII
  • R 15 , R 17 and R 19 are different or preferably the same and are each selected from
  • R 16 , R 18 and R 20 are each identically or differently selected from CH 2 -OH, CH 2 -O-R 21 or hydrogen, although preferably at least one of the R 15 to R 20 variables being other than hydrogen, R 21 is in each occurrence the same or different and selected from
  • Ci-C 4 -alkyl for example ethyl, n-propyl, n-butyl, isopropyl and especially methyl, (CH 2 CH 2 O) m -H where m is selected from integers in the range from 1 to 25.
  • a particularly preferred embodiment of the present invention utilizes such melamine derivatives of the general formula VII as have from three to five of the R 15 to R 20 variables equal to hydrogen and from one to three of the R 15 to R 20 variables selected from CH2-O-R 21 , where m is an integer from 1 to 3.
  • Melamine derivatives of the general formula VIII are known per se. Melamine derivatives of the formula VII are generally not present pure in the sense of conforming to one defined formula; it is customary to observe intermolecular rearrangements, i.e., trans- acetalization reactions and trans-aminalization reactions, and also to some extent con- densation reactions and elimination reactions.
  • the above-indicated formula VII is to be understood as defining the stoichiometric ratios of the variables of the R 15 to R 20 radicals and as also encompassing intermolecular rearrangement products and condensation products.
  • non-hydrophilized and hydrophilicized isocyanurates are iso- cyanurates for example of the general formula IX
  • R 22 variables are different or preferably the same and represent for example (CHb) n -NCO, where n is an integer in the range from 2 to 20 and preferably from 4 to 12, very particular preference being given to all R 22 variables being the same and n representing 6, and which - in the case of the hydrophilized isocyanurates - may have been reacted with from one to three equivalents of polyalkylene oxides such as for example polypropylene oxide or preferably polyethylene oxide.
  • polyalkylene oxides such as for example polypropylene oxide or preferably polyethylene oxide.
  • polyglycidyl ethers (e3) having from 2 to 5 glycidyl groups per molecule and preferably from 2 to 4 glycidyl groups per molecule are pentaerythrityl triglycidyl ether and glyceryl 1 ,3-diglycidyl ether and mixtures thereof.
  • carbodiimides are dicyclohexylcarbodiimide and also the systems described in the patent applications EP-A 1 002 001 , DE-A 199 54 500 and DE-A 100 00 656.
  • urea or urea derivatives (e5) which may if appropriate be converted to aminals or hemiaminals, are: unmodified or multiply, especially singly, doubly, triply or quadruply, alkylolated, especially methylolated and also alkoxyalkylolated, and especially methoxymethylolated urea compounds and their di-, tri- and tetramers or oli- gomeric or polymeric, linear, branched or cyclic precondensates.
  • alkylolated urea compounds as di-/tri-tetrameric or oligomeric or polymeric, linear or branched or cyclic addition/condensation products of urea and multiply functional alkylaldehydes, especially glyoxal and their alkoxylated and especially methoxylated compounds.
  • fixing agent (e) is identical to resin (a). In another embodiment, fixing agent (e) is different from resin (a).
  • Aqueous formulations used in step (C) of the present invention may have a solids content in the range from 10% to 70% by weight and preferably in the range from 30% to 50% by weight.
  • the wet pickup may be chosen such that step (C) results in a wet pickup in the range from 25% by weight to 200% by weight and preferably in the range from 60% to 190% by weight.
  • the temperature for practicing step (C) of the present invention is in itself not critical.
  • the temperature may be in the range from 10 to 60 0 C and preferably in the range from 15 to 30 0 C.
  • aqueous formulation used in step (C) may have a pH in the range from 2 to 9, and preferably in the range from 3.5 to 7.5.
  • Step (C) of the present invention is in one embodiment of the present invention carried out in common machines used for the finishing of textiles, for example pad-mangles or foulards.
  • Preference is given to vertical textile feed pad-mangles or foulards, where the essential element is two rollers in press contact with each other, through which the printed substrate is led.
  • the aqueous formulation containing at least one binder is filled in above the rollers and wets the printed substrate. The pressure causes the printed substrate to be squeezed off and ensures a constant add-on.
  • printed substrate is first led through a dip bath and then upwardly through two rolls in pressed contact with each other.
  • the pad- mangles are also said to have a vertically upward textile feed.
  • Pad-mangles and foulards are described for example in Hans-Karl Rouette, " Handbuch der Textilveredlung " , Irishr fraverlag 2003, pages 618 to 620.
  • Aftertreatment in accordance with the present invention may also be accomplished for example by single or multiple spraying, bedrizzling, overpouring or printing.
  • Aqueous formulations for the purposes of the present invention may - in addition - comprise one or more organic solvents, for example alcohols such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, acetic acid, n-butanol, isobutanol, n-hexanol and isomers, n-octanol and isomers, n-dodecanol and isomers.
  • organic solvents for example alcohols such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol mono-n-butyl
  • Organic solvents may comprise from 1 % to 40% by weight and preferably from 2% to 25% by weight of the continuous phase of aqueous formulation used in accordance with the present invention.
  • aqueous formulations is to be understood as referring to such formulations where the continuous phase consists predominantly or, at the extreme, exclusively of water.
  • the aftertreated substrate from polypropylene can be dried after having performed step (C). Drying may be accomplished for example at temperatures in the range from 20 to 120 0 C.
  • Drying may be carried out at atmospheric pressure for example. It may also be carried out at reduced pressure, for example at a pressure in the range from 1 to 850 mbar.
  • Drying may utilize a heated or unheated stream of gas, in particular a heated or unheated stream of an inert gas such as nitrogen for example.
  • suitable temperatures range for example from 30 to 200 0 C, preferably from 120 to 150°C.
  • Step (C) and the drying operation may be followed by a thermal treatment, also referred to as tempering in the context of the present invention, as a continuous operation or as a batch operation.
  • the duration of the tempering treatment can be chosen within wide limits.
  • the tempering treatment can typically be carried out for a duration in the range from about 1 second to 30 minutes and especially up to 3 minutes.
  • a tempering treatment is carried out by heating to temperatures of 120 0 C up to 180 0 C, preferably in the range from 150 to 170 0 C. It is of course necessary to adapt the temperature of the tempering treatment to the sensitivity of the material of which the surface is made that has been treated according to the present invention.
  • Hot air drying is an example of a specific suitable method of tempering.
  • substrate from polypropylene is (A) pretreated with at least one aqueous pretreatment liquor comprising
  • Resins (a) and thickeners (b) are each as defined above.
  • Aqueous pretreatment liquors may comprise one or more polycationic compounds as component (c).
  • polycationic compounds include for example cationic homopolymers or copolymers.
  • Preferred polycationic compounds are polyvinylamines, for example having Fikentscher K values in the range from 15 to 60, polyethylenimines, for example having an M n molecular weight in the range from 5,000 to 1 ,000,000 g/mol, homo- or copoly- mers of diallyldialkylammonium monomers, such as diallyldimethylammonium chloride, cationic acrylates and acrylamides such as acryloyloxyethyldimethylammonium chloride or acrylamidoethyldimethylammonium chloride, quaternary vinylpyridines such as methylvinylpyridine chloride, polyalkylamine polymers and copolymers, also polyal- lylamine hydrochloride, allylamine hydrochloride-diallylamine hydrochloride copolymer, N-vinylacryloylamidine hydroch
  • Preferred polycationic compounds (c) are homo- or copolymers of diallyldialkylammonium monomers, such as polydiallyldimethylammonium chloride (poly DAD MAC), polydiallyldiethylammonium chloride (polyDADEAC), polydiallyldimethylammonium bromides (polyDADMABs), polydiallyldiethylammonium bromide (polyDADEAB), particular preference is given to polymers or copolymers of diallyldimethylammonium chloride and especial preference is given to diallyldimethylammonium chloride homopoly- mer (polyDADMAC).
  • poly DAD MAC polydiallyldimethylammonium chloride
  • polyDADEAC polydiallyldiethylammonium chloride
  • polyDADMABs polydiallyldimethylammonium bromides
  • polyDADEAB polydiallyldiethylammonium bromide
  • Copolymers of the monomers mentioned may also comprise nonionic monomers, for example vinylpyrrolidone, (partially saponified) vinyl acetate or hydroxy(meth)acrylate, as interpolymerized comonomers.
  • nonionic monomers for example vinylpyrrolidone, (partially saponified) vinyl acetate or hydroxy(meth)acrylate, as interpolymerized comonomers.
  • aqueous pretreatment liquors comprise polymers or copolymers of diallyldialkylammonium monomers, especially diallyldimethylammonium chloride homopolymer, as polycationic compounds (C), at least one mela- mine derivative as resin (a) and one or more associative thickeners of the formula I, Il and/or III as thickeners (b).
  • aqueous pretreatment liquors may comprise additives as a component (d).
  • Additives are for example aldehyde scavengers, defoamers, emulsifiers, solvents, biocides, deaerators and wetting agents.
  • Useful aldehyde scavengers include for example urea and carbamates.
  • Useful defoamers include for example silicone defoamers such as for example those of the formula HO-(CH2)3-Si(CH3)[OSi(CH3)3]2. Silicone-free defoamers are also suitable, examples being multiply alkoxylated alcohols, for example fatty alcohol alkoxylates, preferably 2- to 50-tuply ethoxylated preferably unbranched Cio-C2o-alkanols, un- branched Cio-C2o-alkanols and 2-ethylhexan-1-ol.
  • silicone defoamers such as for example those of the formula HO-(CH2)3-Si(CH3)[OSi(CH3)3]2.
  • Silicone-free defoamers are also suitable, examples being multiply alkoxylated alcohols, for example fatty alcohol alkoxylates, preferably 2- to 50-tuply ethoxylated preferably unbranched Cio-C2o-alkanols, un
  • Useful emulsifiers include for example cationic, anionic, zwitterionic and nonionic surfactants.
  • Nonionic surfactants are particularly useful, examples being multiply and es- pecially 5- to 10O-tuply alkoxylated fatty alcohols.
  • Useful biocides include for example 1 ,2- benzisothiazolin-3-one (“BIT”) (commercially available as Proxel® brands from Avecia Lim.) and its alkali metal salts; useful biocides also include 2-methyl-2H-isothiazole-3 (“MIT”) and 5-chloro-2-methyl-2H-isothiazol-3-one (“CIT”).
  • BIT 1 ,2- benzisothiazolin-3-one
  • MIT 2-methyl-2H-isothiazole-3
  • CIT 5-chloro-2-methyl-2H-isothiazol-3-one
  • Useful deaerators are for example those based on polyethersiloxane copolymers, for example H-(EO)a-O-(CH2)3-Si(CH3)[OSi(CH3)3]2, where a for example represents an integer in the range from 1 to 10 and EO represents OCH2CH2.
  • Useful wetting agents include for example nonionic, anionic or cationic surfactants, especially ethoxylation and/or propoxylation products of fatty alcohols or propylene oxide-ethylene oxide block copolymers, ethoxylated or propoxylated fatty or oxo alcohols, also ethoxylates of oleic acid or alkylphenols, alkylphenol ether sulfates, alkyl- polyglycosides, alkyl phosphonates, alkylphenyl phosphonates, alkyl phosphates or alkylphenyl phosphates.
  • nonionic, anionic or cationic surfactants especially ethoxylation and/or propoxylation products of fatty alcohols or propylene oxide-ethylene oxide block copolymers, ethoxylated or propoxylated fatty or oxo alcohols, also ethoxylates of oleic acid or alkylphenols, alkylphenol ether sulf
  • a further aspect of the present invention comprises substrates from polypropylene obtainable by the present invention's process described above.
  • Inventive substrates from polypropylene are notable not only for particular brilliance of the color and the contours and particularly good adhesion and hence fastness of the print, for example for particularly good rubfastnesses, wetrubfastnesses and washfastnesses, even after repeated bending or folding, but also for a particularly pleasant hand.
  • nonvolatiles 42.5% by weight (determined by 2 h drying in a drying cabinet at 120°C), H 2 O by Karl Fischer: 3.7% by weight, dynamic viscosity ⁇ : 850 mPa-s, determined using a plate-cone viscometer.
  • Non-v. nonvolatiles (determined by 2 h drying in a drying cabinet at 120 0 C)
  • DEG diethylene glycol.
  • ⁇ determined at 23°C
  • Component (b): b.1 see hereinbelow
  • b.1 associative thickener, reaction product of hexamethylene diisocyanate (HDI) with ethoxylated n-CisH37OH of M w 10,000 g/mol, the ethoxylated fatty alcohol being used in an excess of 50 mol%, based on isocyanate groups;
  • c.1 polyethyleneimine, M w 25,000 g/mol c.2: diallyldimethylammonium chloride homopolymer;
  • M w 10,000 g/mol d.1 tri-n-butyl phosphate defoamer d.2: 20% by weight of solution of 1 ,2-benzisothiazolin-3-one in propylene glycol d.3: dispersing binder according to Example IV.
  • Table 2 Inventive pretreatment liquors
  • the hereinbelow recited inks for the ink jet process were produced by mixing the constituents identified in table 4. Initially, mix components M1 to M3 were produced by introducing each of the constituents recited in table 3 into a ball mill, making up to 100 ml with distilled water in each case and dispersing. A glass beaker was then used as a location to formulate ink T1 from mix component M1 and the ingredients of table 5, ink T2 from mix component M2 and the ingredients of table 4 and ink T3 from mix component M3 and the ingredients of table 5, making up to 100 ml with distilled water each time.
  • Biocide 1 20% by weight of solution of 1 ,2-benzisothiazolin-3-one in dipropylene glycol
  • a mixture 11.3.1 was prepared by dispersing 7.8 g of freshly distilled acrylic acid, 58.2 g of styrene, 252 g of n-butyl acrylate 282 g of ethyl acrylate
  • Mixture 11.3.2 was prepared by dissolving 2.4 g Of Na 2 S 2 Os in 100 ml of distilled water.
  • Mixture 11.3.3 was prepared by dissolving 1.2 g of HO-CH 2 SO 2 Na in 100 ml of distilled water.
  • a 5-leter-vessel was charged with 300 g of distilled water and 13.6 g of a 33 % by weight seed of polystyrene (average diameter 30 nm, in water). A suspension was formed. Nitrogen was bubbled through the suspension over a period of 15 minutes. Then, the suspension was heated to 75°C. The addition of mixtures 11.3.1 , II.3.2 and II.3.3 was started simultaneously. The addition of mixture 11.3.1 was completed within 3 hours, the addition of mixtures II.3.2 and II.3.3 was completed within 3 hours and 15 minutes. During addition of said mixtures and during 30 minutes after having finished addition of mixture 11.3.2, stirring at 75°C was continued for additional 30 minutes. Then, 3 g of a 25% by weight aqueous solution of ammonia was added.
  • Solids contents 38.7% by weight, pH value: 7, dynamic viscosity: 30 mPa-s (23°C). Average particle diameter: maximum at 146 nm. Glass transition temperature: -22°C (DSC).
  • Comparative example D3 of EP 1 001 002 B1 but diluted with water up to a solids con- tent of 30% by weight.
  • Nonwoven from polypropylene PP- 1 was treated with a pretreatment liquor as per ta- ble 2 on a pad-mangle from Mathis (model No. HVF63003).
  • the nip pressure of the rolls was 2.2 bar, resulting in a wet pickup of 60%.
  • the application speed was 1 m/min.
  • the pretreated fabric was subsequently dried at 90 0 C.
  • Nonwovens from polypropylene pretreated according to the present invention were obtained.
  • Pretreated polypropylene nonwovens were each printed with an ink on a Mi- maki TX 1600 S printer. After drying at room temperature, printed nonwovens were aftertreated on a foulard with either an aqueous liquor, containing
  • pick-up was set to 175% by weight, then fixing was performed at 120 0 C for 2 minutes.
  • Pretreated and printed fabrics according to the present invention possessed excellent hand and brilliant colors.
  • the wash fastness and water fastness of inventively colored PP.1 and PP.2 was excellent as well:

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

La présente invention concerne un procédé de coloration d'un substrat de polypropylène, ledit procédé comprenant (A) le prétraitement d'un substrat de polypropylène par une liqueur aqueuse de prétraitement qui comprend (a) au moins une résine sélectionnée parmi les dérivés de mélamine, la diméthyloldihydroxyéthylène urée (DMDHEU) et des dérivés de DMDHEU et (b) au moins un épaississant, (B) l'impression dudit substrat prétraité à l'aide d'une opération à jet d'encre et ensuite (C) le post-traitement dudit substrat par une formulation aqueuse qui comprend au moins un liant.
PCT/EP2007/061608 2006-10-30 2007-10-29 Procédé de coloration de substrats de polypropylène Ceased WO2008052962A1 (fr)

Applications Claiming Priority (2)

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EP06123178 2006-10-30
EP06123178.3 2006-10-30

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WO2008052962A1 true WO2008052962A1 (fr) 2008-05-08

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014127050A1 (fr) * 2013-02-12 2014-08-21 Sensient Colors Llc Compositions d'encre
US8814318B2 (en) 2010-06-14 2014-08-26 Hewlett-Packard Development Company, L.P. Printing method with pre-treatment composition
US9278515B2 (en) 2010-06-14 2016-03-08 Hewlett-Packard Development Company, L.P. Printing method
CN105755723A (zh) * 2016-03-21 2016-07-13 山东黄河三角洲纺织科技研究院有限公司 一种聚酰胺-酯面料的仿旧加工方法
US9493685B2 (en) 2010-06-14 2016-11-15 Hewlett-Packard Development Company, L.P. Pre-treatment composition
US9505024B2 (en) 2011-12-19 2016-11-29 Hewlett-Packard Development Company, L.P. Method of producing a printed image on a pre-treated, low-porous or non-porous medium
US10144830B2 (en) 2011-12-19 2018-12-04 Hewlett-Packard Development Company, L.P. Pretreatment fluids with ammonium metal chelate cross-linker for printing media

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8814318B2 (en) 2010-06-14 2014-08-26 Hewlett-Packard Development Company, L.P. Printing method with pre-treatment composition
US9278515B2 (en) 2010-06-14 2016-03-08 Hewlett-Packard Development Company, L.P. Printing method
US9493685B2 (en) 2010-06-14 2016-11-15 Hewlett-Packard Development Company, L.P. Pre-treatment composition
US9505024B2 (en) 2011-12-19 2016-11-29 Hewlett-Packard Development Company, L.P. Method of producing a printed image on a pre-treated, low-porous or non-porous medium
US10144830B2 (en) 2011-12-19 2018-12-04 Hewlett-Packard Development Company, L.P. Pretreatment fluids with ammonium metal chelate cross-linker for printing media
WO2014127050A1 (fr) * 2013-02-12 2014-08-21 Sensient Colors Llc Compositions d'encre
US9844949B2 (en) 2013-02-12 2017-12-19 Sensient Colors Llc Ink compositions
CN105755723A (zh) * 2016-03-21 2016-07-13 山东黄河三角洲纺织科技研究院有限公司 一种聚酰胺-酯面料的仿旧加工方法

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