EP0965680A1 - Wässrige Dispersionen, ihre Herstellung und Verwendung - Google Patents

Wässrige Dispersionen, ihre Herstellung und Verwendung Download PDF

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Publication number
EP0965680A1
EP0965680A1 EP98810558A EP98810558A EP0965680A1 EP 0965680 A1 EP0965680 A1 EP 0965680A1 EP 98810558 A EP98810558 A EP 98810558A EP 98810558 A EP98810558 A EP 98810558A EP 0965680 A1 EP0965680 A1 EP 0965680A1
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EP
European Patent Office
Prior art keywords
meth
poly
aqueous
acrylamide
mixture
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EP98810558A
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German (de)
English (en)
French (fr)
Inventor
Erfindernennung liegt noch nicht vor Die
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Clariant International Ltd
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Clariant International Ltd
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Application filed by Clariant International Ltd filed Critical Clariant International Ltd
Priority to EP98810558A priority Critical patent/EP0965680A1/de
Priority to PCT/IB1999/001119 priority patent/WO1999066118A1/en
Priority to US09/720,065 priority patent/US6736865B1/en
Priority to BRPI9911275-2A priority patent/BR9911275B1/pt
Priority to TR2000/03744T priority patent/TR200003744T2/xx
Priority to AT99923804T priority patent/ATE385270T1/de
Priority to PT99923804T priority patent/PT1090179E/pt
Priority to JP2000554917A priority patent/JP4302892B2/ja
Priority to ES99923804T priority patent/ES2299247T3/es
Priority to IDW20002633A priority patent/ID26638A/id
Priority to DE69938079T priority patent/DE69938079T2/de
Priority to EP99923804A priority patent/EP1090179B1/en
Publication of EP0965680A1 publication Critical patent/EP0965680A1/de
Priority to ZA200007035A priority patent/ZA200007035B/en
Priority to HK01105840A priority patent/HK1035218A1/xx
Withdrawn legal-status Critical Current

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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General 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
    • D06P1/44General 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
    • D06P1/64General 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 low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/651Compounds without nitrogen
    • D06P1/6515Hydrocarbons
    • D06P1/65162Hydrocarbons without halogen
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/02Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M7/00Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General 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
    • D06P1/0036Dyeing and sizing in one process
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General 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
    • D06P1/44General 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
    • D06P1/52General 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
    • D06P1/5207Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/5214Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
    • D06P1/5221Polymers of unsaturated hydrocarbons, e.g. polystyrene polyalkylene
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General 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
    • D06P1/44General 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
    • D06P1/52General 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
    • D06P1/5207Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/5214Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
    • D06P1/5242Polymers of unsaturated N-containing compounds
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General 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
    • D06P1/44General 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
    • D06P1/52General 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
    • D06P1/5207Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/525Polymers of unsaturated carboxylic acids or functional derivatives thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General 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
    • D06P1/44General 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
    • D06P1/52General 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
    • D06P1/5207Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/525Polymers of unsaturated carboxylic acids or functional derivatives thereof
    • D06P1/5257(Meth)acrylic acid
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/40Reduced friction resistance, lubricant properties; Sizing compositions

Definitions

  • Wax dispersions are known from GB-A 2282153, which are particularly suitable as electrolyte-resistant anti-wrinkle agents (lubricants).
  • lubricants are particularly suitable as electrolyte-resistant anti-wrinkle agents (lubricants).
  • the invention relates to the preparations (L), their preparation and their use.
  • waxes can generally be used as waxes (a).
  • Any hydrocarbon waxes (a1) containing carboxy groups are generally suitable synthetic waxes and / or oxidatively modified mineral and / or synthetic hydrocarbon waxes, which have a wax structure, e.g. by copolymerization (e.g. block copolymerization or mixed copolymerization) of olefins, in particular ethylene or propylene comonomers containing carboxylic acid groups, in particular (meth) acrylic acid and / or maleic acid, or by graft polymerization, or oxidation products of hydrocarbon waxes or waxes containing carboxylic acid groups which may be oxidative are synthesized, such as Fischer-Tropsch waxes and their partial saponification products.
  • copolymerization e.g. block copolymerization or mixed copolymerization
  • olefins in particular ethylene or propylene comonomers containing carboxylic acid groups, in particular (meth) acrylic acid and / or maleic acid,
  • the hydrocarbon waxes (a1) containing carboxylic acid groups are preferably oxidized and optionally partially hydrolyzed hydrocarbon waxes and generally include any synthetic and / or mineral waxes, which still have a wax structure in the oxidized form, in particular oxidized micro waxes or oxidized polyolefin waxes (mainly polyethylene waxes) or waxes, which are optionally synthesized directly in oxidized form, especially Fischer-Tropsch waxes, and also their oxidation waxes, the oxidized waxes mentioned, especially the oxidized polyolefin waxes and the Fischer-Tropsch waxes, if appropriate can be partially saponified.
  • any synthetic and / or mineral waxes which still have a wax structure in the oxidized form, in particular oxidized micro waxes or oxidized polyolefin waxes (mainly polyethylene waxes) or waxes, which are optionally synthesized directly in oxidized form, especially Fischer-Tropsch
  • Waxes are generally known and can be characterized by common parameters such as the needle penetration (e.g. according to ASTM-D 1321 or -D 5), the solidification point, the dropping point, the Density, the acid number or / and possibly also the saponification number.
  • Waxes (a1) are preferred to those whose needle penetration is 20 20 dmm, especially those whose needle penetration is in the range from 0.1 to 10 dmm, preferably 0.2 to 5 dmm, and their Acid number is in the range from 5 to 70, preferably 9 to 50.
  • the density of the waxes (a1) lies advantageously in the range from 0.90 to 1.1, preferably 0.92 to 1.02, in particular 0.94 to 0.99.
  • the waxes mentioned are especially the oxidized polyethylene waxes, primarily oxidized Low-pressure polyethylene, preferred, especially those with a needle penetration in the range of 0.2 up to 5 dmm.
  • the waxes (a2) are not modified, i.e. there are hydrocarbon waxes in which none functional groups or heteroatoms have been inserted.
  • (a2) e.g. non-oxidized micro waxes or paraffin waxes can be used.
  • Paraffin waxes with a dropping point of ⁇ 40 ° C. come as (a2) up to 110 ° C, preferably 50 to 105 ° C, in particular table paraffin.
  • (a2) may be present, it is preferred that (a1) not be blended with (a2) will, i.e. that the entire wax (a) consists essentially only of (a1). Especially when the Dispersions (L) are used as wet lubricants in nozzle dyeing machines, it is preferred that the entire wax (a) consists essentially only of (a1).
  • the proportion of (b ') in (b1) is advantageously in the range from 50 to 100 mol%, preferably from 60 to 95 mol%, the remainder to 100 mol%. i.e. 50 to 0 mol%, preferably 40 to 5 mol%, in consists essentially of (b '').
  • the proportion of (b ') in (b2) is advantageously in the range from 50 to 100 mol%, preferably from 80 to 100 mole%, the remainder to 100 mole%. i.e. 50 to 0 mol%, preferably 20 to 0 mol%, in consists essentially of (b '').
  • (meth) acrylamide (co) polymers with very high molecular weight are used as (b1), which are referred to here as macro (co) poly (meth) acrylamides.
  • the average molecular weight M W of (b1) can be of any size, for example n can be in the range from 10 to 80, primarily n is in the range from 10 to 40, preferably 12 to 30, particularly preferably 15 to 25. According to a particular embodiment of the invention n ⁇ 16.
  • Polymers are used as (b2) which have a lower molecular weight than (b1), namely in which the average molecular weight is ⁇ 10 million.
  • the average molecular weight is advantageous M W of (b2) in the range from 100000 to 8 ⁇ 10 6 , preferably in the range from 200000 to 5 ⁇ 10 6 .
  • the polymers (b) are known or can be prepared by methods known per se.
  • the copolymers from (b ') and (b' ') can be prepared by conventional copolymerization processes are produced, dicarboxylic acids such as e.g. Maleic acid, optionally also as cyclic Anhydrides can be used.
  • dicarboxylic acids such as e.g. Maleic acid, optionally also as cyclic Anhydrides can be used.
  • Those in which (b '') the comonomer from acrylic acid or methacrylic acid can also by hydrolysis of a portion of the amide groups corresponding homopolymers or copolymers that only consist of acrylamide and / or methacrylamide units is made.
  • the weight ratio (b2) / (b1) can vary within a wide range. Per part by weight (b1) e.g. 0 to 30, advantageously 0 to 20, preferably 0 to 10 parts by weight (b2) are used. If (b2) is used, at least 1 part by weight (b2) per part by weight (b1) is advantageously used.
  • the carboxy groups can be in the form of the free acid and / or in the form of salts, cations known per se, preferably hydrophilizing cations, being suitable for salt formation, for example alkali metal cations (for example sodium, potassium) or ammonium cations ⁇ for example unsubstituted ammonium, mono- , Di- or tri- (C 1-2 -alkyl) -ammonium, mono-, di- or tri- (C 2-3 -hydroxy-alkyl) -ammonium, mono-, di- or tri - [(C 1 -2- alkoxy) - (C 2-3 alkyl)] - ammonium or morpholinium ⁇ .
  • alkali metal cations for example sodium, potassium
  • ammonium cations for example unsubstituted ammonium, mono- , Di- or tri- (C 1-2 -alkyl) -ammonium, mono-, di- or tri- (C 2-3 -hydroxy-alkyl)
  • the weight ratio (b) / (a) is e.g. in the range from 1: 1 to 1: 200, advantageously 1: 2 to 1: 100, preferably 1: 3 to 1:40.
  • the surfactants (d1), (d2) and (d3) generally have the character of dispersants.
  • the HLB value of the surfactants (d1) is advantageously in the range from 7 to 16, preferably in the range from 8 to 15.
  • R 12 to 22 Contains carbon atoms, especially 14 to 22 carbon atoms, preferred.
  • anionic surfactants (d2) there are generally known acids with a surfactant character considered as such as dispersants, e.g. as emulsifiers or as detergents, usually Find use.
  • Such surfactant anionic compounds are known in the art and described in numerous technical literature, e.g. in "Surfactant Science Series", Volume 7 ("Anionic Surfactants ").
  • anionic surfactants come into consideration that have a lipophilic Contain residue (especially the residue of a fatty acid or an aliphatic hydrocarbon residue a fatty alcohol) of, for example, 8 to 24 carbon atoms, advantageously 12 to 22 carbon atoms, contains in particular 14 to 22 carbon atoms and can be aliphatic or araliphatic and wherein the aliphatic radicals can be linear or branched, saturated or unsaturated.
  • the lipophilic residues are purely aliphatic and unsaturated
  • Sulfonic acids the lipophilic residues preferably saturated purely aliphatic or araliphatic residues are, in particular as described above for the non-ionic surfactants.
  • the carbon or Sulphonic acid group can be attached directly to the hydrocarbon residue (especially as Fatty acid, e.g. in the form of soaps, or as alkanesulfonic acid) or via at least one a heteroatom interrupted bridge, which is preferably aliphatic.
  • the introduction of Carboxy groups can e.g. by carboxyalkylation of hydroxy groups or monoesterification a hydroxy group with a dicarboxylic anhydride, e.g.
  • oxiranes for the oxyalkylation primarily ethylene oxide, propylene oxide and / or butylene oxide and optionally styrene oxide, and preferably at least 50 mol% of the oxiranes used is ethylene oxide; for example, these are Addition products of 1 to 12 moles of oxirane with 1 mole of hydroxy compounds, especially as above Starting product called oxyalkylation.
  • Haloalkane carboxylic acids are primarily used for carboxyalkylation used, advantageously those in which the halogenoalkyl radical has 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms, contains halogen primarily for chlorine or bromine stands and the acid group can optionally be in salt form.
  • a carboxy group can e.g. also be introduced by monoesterification of an aliphatic dicarboxylic acid, e.g. by Reaction of a hydroxy compound with a cyclic anhydride, e.g. with phthalic anhydride or an aliphatic anhydride with 2 or 3 carbon atoms between the two carboxy groups, e.g.
  • Analog can by esterification e.g. phosphoric acid or sulfuric acid partial ester groups are also introduced.
  • the sulfonic acids are essentially sulfonation products from paraffins (e.g. produced by sulfochlorination or sulfoxidation), of ⁇ -olefins, of alkylbenzenes and of unsaturated Fatty acids into consideration.
  • the anionic surfactants are advantageously used in the form of salts, hydrophilizing cations are particularly suitable for salt formation, in particular Alkali metal cations (e.g. sodium, potassium) or ammonium cations [e.g.
  • alkaline earth metal cations e.g. calcium or magnesium
  • anionic mentioned Surfactants (d2) which are free of ester groups are preferred, primarily soaps, in particular amine soaps, and the carboxymethylation products of oxyethylated fatty alcohols and the sulfonic acids, preferably in salt form as mentioned above, especially as alkali metal salts.
  • amphoteric surfactants (d3)
  • those that are introduced by introducing at least one anionic group into a cationic surfactant containing a reactive hydroxy or amino group are available [e.g. by Carboxyalkylation of amino groups, by esterification of hydroxy groups for the introduction of Sulfato or phosphato groups, by monoacylation of amino or hydroxy groups Cyclic dicarboxylic anhydrides analogous to (d2) described above, by sulfomethylation of amino groups, e.g.
  • Suitable cationic surfactants as starting materials well-known compounds, e.g. Fettamines, Fettaminoalkylamine and amidation products of alkylenediamines or polyalkylenepolyamines with a fatty acid residue, or acylation products of alkanolamines or alkanolaminoalkylamines, and their oxyalkylation products and / or quaternization products.
  • the fat residues in (d3) are e.g. as described for (d1) above.
  • alkylene bridges between two nitrogen atoms in the alkylenediamines, polyallcylenepolyamines and alkanolaminoalkylamines are advantageously those with 2 to 6, preferably 2 to 4, carbon atoms; the alkanol groups in the alkanolamines and Alkanolaminoalkylamines are advantageously those with 2 or 3 carbon atoms.
  • Preferred Alkylenediamines, polyamines, alkanolamines and alkanolaminoalkylamines are ethylenediamine, Propylene diamine, N, N-dimethylaminopropylamine, hexamethylene diamine, diethylene triamine, ethylene propylene triamine, Dipropylenetriamine, monoethanolamine and 3- ( ⁇ -hydroxyethylamino) propylamine.
  • ethylene oxide is preferably added, e.g. 2 to 20 moles of ethylene oxide per mole Amino compound, or per mole of fat residue.
  • the surfactants (d) are preferably free of easily ridable groups, in particular ester groups.
  • the surfactants (d1), (d2) and (d3) are dispersants prefers.
  • (d) consists exclusively of (d2).
  • the surfactants (d) are expediently used in amounts which are sufficient for the waxes (a) can be well dispersed in the aqueous phase and an aqueous dispersion of (a) can arise.
  • the weight ratio (d) / (a) is e.g. in the range from 10/100 to 80/100, preferably 20/100 to 60/100.
  • Suitable crosslinking agents (c) are those which are capable of reacting with or crosslinking amide groups of (b), in particular low molecular weight aliphatic compounds, for example an aliphatic aldehyde or an aliphatic diamine, in which both amino groups are primary.
  • Suitable (c) aliphatic crosslinking agents are, for example, those with up to six carbon atoms, for example formaldehyde and acetaldehyde, and alkylenediamines with 2 to 6 carbon atoms, for example of the formula H 2 N ⁇ (CH 2 ) p ⁇ NH 2 where p is 2 to 6, among which preferred are those wherein p is 2 or 3.
  • crosslinking agents (c) are advantageously used in such amounts that they are sufficient existing amide groups in (b) can be at least partially crosslinked.
  • the molar ratio of (c) to the amide groups of (b) present is advantageously in the range from 0 to 10, preferably 0.01 to 5.
  • the aldehydes are preferred.
  • Protective colloids (e1) here are both highly hydrophilic polymers and highly hydrophilic surfactants meant that a protective effect on the aqueous two-phase system, especially on the dispersed Particles, exercise.
  • These highly hydrophilic surfactants differ from (d) in particular in that they are not dispersants per se, insofar as they alone are not suitable for the Disperse waxes finely, but have a stabilizing effect on the (d) -containing dipersion.
  • Protective colloids (e1) are any highly hydrophilic products known per se Consider, preferably non-ionic or amphoteric compounds.
  • Non-ionic protective colloids are, for example, to increase the hydrophilicity, chemically modified polysaccharides [eg hydroxy- (C 1-4 -alkyl) - and / or carboxymethyl- and optionally methyl-modified polysaccharides], hydrophilic vinyl polymers (eg polyvinyl alcohols or polyvinylpyrrolidones) or oxethylation products of higher aliphatic alcohols.
  • the HLB of the non-ionic protective colloids is advantageously> 15, preferably ⁇ 16.5, especially in the range from 16.5 to 19.
  • q preferably denotes 30 to 70, in particular 35 to 60.
  • Suitable amphoteric protective colloids are e.g. those which are produced analogously to (d3) above may differ from (d3) by a higher hydrophilicity, e.g. through a polyglycol ether chain, a quaternization or protonation, in relation to the lipophilic residue.
  • They are suitable in particular quaternary amphoteric surfactants, which are a fat residue and a preferably quaternary Ammonium group and an anionic radical and optionally a polyethylene glycol ether chain contain, especially those with a molecular weight of the internal salt form in the range of 300 to 3000 and wherein the fat residue advantageously contains 8 to 24, preferably 12 to 18 carbon atoms.
  • a protective colloid (e1) for example, per 100 parts by weight (a) 5 to 50, advantageously 10 up to 40 parts by weight, preferably 15 to 35 parts by weight of protective colloid (e1).
  • the dispersions (L) as (e) may also contain a hydrotrope (e2), which also can serve as a solubilizer or antifreeze.
  • hydrotrope or anti-freeze products known per se can be used, in particular non-ionic, predominantly low molecular weight amides (e.g. acetamide or urea) and aliphatic oligohydroxy compounds [e.g. with 2 to 12, preferably 3 to 10, in particular 4 to 8, carbon atoms , for example glycerol, hexylene glycol and / or mono- or oligo- (C 2-4 -alkylene) -glycols] or their mono- (C 1-4 -alkyl) ether.
  • non-ionic, predominantly low molecular weight amides e.g. acetamide or urea
  • aliphatic oligohydroxy compounds e.g. with 2 to 12, preferably 3 to 10, in particular 4 to 8, carbon atoms , for example glycerol, hexylene glycol and / or mono- or oligo- (C 2-4 -alkylene) -glycols] or their mono- (
  • the Weight ratio of (e2) to (L) is advantageously in the range of 0.5 to 15 parts by weight (e2) per 100 parts by weight (L), preferably in the range of 1 to 10 parts by weight (e2) per 100 parts by weight (L).
  • the dispersions (L) to be used according to the invention can additionally at least contain an additive (f), which is expediently an anti-bacterial agent or Is microbicid.
  • an additive e.g. an anti-bacterial agent or Is microbicid.
  • Fungicides and bactericides come into consideration as (f), e.g. for sale Products that can be used in the recommended concentrations.
  • the dispersions (L) according to the invention can be mixed in a very simple manner by suitable mixing of the components are produced, in particular in that an aqueous dispersion (w) of (a), which also contains (d), mixed with an aqueous solution of (b) and, if appropriate, further additives, in particular (c), (e) and / or (f).
  • the aqueous dispersion (w) can be prepared in a very simple manner by e.g. a corresponding (a) melt, which also contains (d) and optionally (e), and which optionally contains one suitable base for salt formation with the carboxy groups has been added (e.g. an alkali metal hydroxide or carbonate and / or an amine, as it corresponds to the above cations), with Diluted water.
  • a suitable base for salt formation with the carboxy groups e.g. an alkali metal hydroxide or carbonate and / or an amine, as it corresponds to the above cations
  • the dispersant system (d) is expediently chosen so that a dispersion of (a) is formed; the Components (c), (e) and / or (f) can be mixed before and / or after the (a) dispersion has been mixed with the (b) solution are added, depending on the convenience.
  • the components (e1) and (e2) are advantageously mixed with the (a) dispersion.
  • Component (c) can be mixed before or after mixing (a) are added with (b).
  • Component (F) is advantageously added last.
  • the pH of the dispersions (L) can vary widely, e.g. in the range of 3 to 12, preferably 4 to 11.
  • the proportions of the respective components and additives, especially the anionic Components and optionally added base can be selected accordingly.
  • a Crosslinking with (c) is particularly favored by alkaline pH values, e.g. in the range of 7.5 to 12, preferably 8 to 11.
  • the aqueous dispersions (L) can be diluted as desired. They are advantageous if possible concentrated, preferably so that a fine aqueous flowable dispersion is formed.
  • the content of (a) + (b) in (L) is e.g. in the range from 0.3 to 40% by weight, advantageously 0.6 to 20% by weight, preferably 1 to 5% by weight.
  • the flow behavior can e.g. according to ASTM-D 1200, 73/050 can be determined.
  • the flow time in the Ford cup (Ford cup) No. 4, at 22 ° C, is e.g. 5 to 60 seconds, advantageously 10 to 45 seconds.
  • the dispersions (L) obtainable as described above are very finely divided; e.g. Dispersions (L) in which the particle size of the dispersed particles is in the range of 0.01 to 10 ⁇ m, preferably 0.05 to 1 ⁇ m.
  • the dispersions (L) can be made as they are have been handled and transported directly, they are particularly very stable and fine dispersions (L) available, even those that are very frost and heat resistant.
  • the dispersions (L) to be used according to the invention are advantageously essentially free of components other than (a), (b), (c), (d), (e), (f), water and any electrolytes [e.g. from the Preparation of (a), (b) or (d) or from pH adjustment].
  • the dispersions (L) described above are used as wet lubricants, i.e. as an aid when treating textile fabrics with treatment agents (T) (e.g. pretreatment, dyeing, optical brightening or post-treatment) under such conditions, under which otherwise Creases can arise or friction can take place in or on the substrate, the Dispersions (L) to be used according to the invention, in particular to prevent stabilization and Marking the wrinkles that develop during the treatment and to prevent harmful ones Serve friction.
  • Such processes are essentially pull-out processes short liquor (liquor / substrate weight ratio e.g. in the range from 3: 1 to 40: 1, usually 4: 1 to 20: 1) under the usual treatment conditions and times (e.g. in the range of 20 minutes up to 12 hours).
  • the dispersions (L), or the components (a) and (b) optionally crosslinked with (c), are in the essentially non-substantive and are generally eliminated by lowering the fleet or / and eliminated by the process-related washing and / or rinsing cycles.
  • the treatment agents (T) are generally textile chemicals, which after the respective treatment of the substrate for which part which is not fixed on the substrate are removed from the substrate again, e.g. by washing and / or rinsing.
  • the main processes in which creases can arise in the textile substrate are meant those in which the wet substrate by exposure and possibly interference various forces tend to fold.
  • the wrinkles in such procedures can arise from stabilization in the course of the treatment process for marking of the kinks, which can lead to the disadvantages mentioned at the beginning.
  • the dispersions (L) serve as anti-crease agents, etc. insofar as it is a sliding of the favor or enable wet fabric or the wet folds and thus a harmful Can prevent stabilization of the creases.
  • the essentially meant those in which the wet substrate due to high running speed, guidance by nozzles or / and changing the direction or / and speed against apparatus parts or adjacent substrate parts rubs.
  • the chafing spots that arise in such processes can in Course of the treatment process to mark them and to impair the physical Lead properties of the substrate.
  • the dispersions (L) serve as Wet lubricant insofar as it slides the wet fabric (especially on adjacent fabric or on metal) favor or enable and thus harmful friction of the substrate can prevent.
  • Treatment processes that cause chafing mainly come Treatments in jet dyeing machines are contemplated, in which the substrate in each Cycle through the nozzle, at which point the relative acceleration and / or on the substrate angular forces are strongest, and wherein the substrate in each cycle of the own position in the fleet is dragged to the nozzle, so that the substrate-against-substrate at the respective points Acceleration or substrate-to-metal acceleration in places cause, which can lead to the abrasion points mentioned.
  • any substrates such as those used in the processes mentioned, are generally suitable can, in particular those which contain modified cellulose fibers, e.g. Cotton, linen, jute, hemp, ramier and modified cotton (e.g. viscose rayon or Cellulose acetates) and cotton-containing fiber mixtures (e.g. cotton / polyester, cotton / polyacrylic, Cotton / polyamide or cotton / polyamide / polyurethane).
  • modified cellulose fibers e.g. Cotton, linen, jute, hemp, ramier and modified cotton (e.g. viscose rayon or Cellulose acetates) and cotton-containing fiber mixtures (e.g. cotton / polyester, cotton / polyacrylic, Cotton / polyamide or cotton / polyamide / polyurethane).
  • the textile substrate can be in any form can be used, as they are treated in the methods mentioned can, e.g.
  • tubular goods as tubular goods, as open textile webs or as semi-finished goods, essentially in strand form, as it is suitable for reel or jet; it can be both knitwear as well Fabrics are used (e.g. fine to coarse simple knitwear or interlock, fine to coarse fabrics, terry goods, velvet and openwork and / or machine-embroidered textiles).
  • the wet lubricants (L) according to the invention are expediently used in such concentrations that that effective prevention of wrinkle marking and chafing in the respective process he follows. They are characterized by their effectiveness and extensiveness and can be very low concentrations show a very high effect; they are advantageous in such Concentrations used that 0.01 to 2 g [(a) + (b)] per liter of liquor, primarily 0.02 to 1.5 g [(a) + (b)] per liter of liquor, preferably 0.03 to 1 g of [(a) + (b)] per liter of liquor, particularly preferred Correspond to 0.04 to 0.5 g [(a) + (b)] per liter of liquor.
  • wet lubricants (L) according to the invention are also distinguished by their great independence from temperature fluctuations and are largely resistant to electrolytes, they can also be used in a very wide range of treatment conditions as they occur in technology for treatment with textile chemicals (T), in particular for pretreatment with (T 1 ), for dyeing or optically brightening with (T 2 ) and for post-treatment with (T 3 ), e.g. with (T 1 ) when boiling (e.g. when beating), when desizing or bleaching, with (T 2 ) in dyeing or optical brightening or also with (T 3 ) in aftertreatment, in particular with cationic fixatives to improve the dyeing fastness (especially the wet fastness), but old when dyeing.
  • Any dye or optical brightener (T 2 ) suitable for the particular substrate and process and for the desired effect can be used for the dyeing or optical brightening.
  • Any suitable dyes can be used for dyeing cellulose-containing substrates, for example reactive dyes, direct dyes, vat dyes, sulfur dyes or also basic dyes, it also being possible to use corresponding additional dyes, in particular, for dyeing substrates from fiber mixtures, in particular from cellulose fibers and synthetic fibers Disperse dyes.
  • the processes can run through any temperature ranges, such as those for the respective substrate and the treatment agent used, as well as due to the apparatus and the desired purpose, e.g. from room temperature (e.g. at the start of dyeing) to HT conditions (e.g.
  • the electrolyte content of the liquors can also be of any type that is normally used for the respective processes, for example in accordance with the concentrations of alkali metal compounds used for boiling, bleaching or desizing, or the alkali metal salt (for example sodium chloride or sodium sulfate) ) concentrations or / and alkali metal hydroxide or carbonate concentrations, such as are used in dyeing with the dyes mentioned, be it as a blend component in commercially available dye preparations and / or as a raking aid in dyeing or optical brightening, or as alkalis in dyeing Sulfur dyes, vat dyes or reactive dyes are used.
  • alkali metal compounds for boiling, bleaching or desizing
  • the alkali metal salt for example sodium chloride or sodium sulfate
  • alkali metal hydroxide or carbonate concentrations such as are used in dyeing with the dyes mentioned, be it as a blend component in commercially available dye preparations and / or as a raking aid in dyeing
  • Post-treatment agents (T 3 ) for increasing the fastness of the dyeings are generally known polycationic products of high charge density, primarily aliphatic condensation products of dicyandiamide or epichlorohydrin with an aliphatic mono- or polyamine or of epichlorohydrin and ammonia, which may be in protonated form available.
  • Such post-treatments advantageously use dispersions (L) in which (b) is essentially free of carboxy groups and (d) consists of (d1), while for pretreatment, coloring and brightening, the dispersion system (d) is preferably used in (L) (d1) or / and (d2).
  • the dispersions (L) are particularly advantageously used as wet lubricants for dyeing, preferably in nozzle dyeing machines, particularly preferred for dyeing cellulose-containing substrates.
  • the wet lubricants (L) according to the invention can be used under the conditions mentioned and come into their own without being impaired.
  • Shear stability of the wet lubricants (L) especially those that do not have non-oxidized waxes (a2) contained, but only from (a1), (b), (d) and optionally (c), (e) and / or (f) in aqueous Dispersion exist, these are particularly suitable as wet lubricants in nozzle dyeing machines before especially in those in which the goods or the fleet have extremely high dynamic loads are exposed, or in which very high shear forces develop in the fleet.
  • the dispersions (L) also have very short liquors, e.g. for fleet / goods ratios ⁇ 15/1, especially ⁇ 10/1, a very good, extremely superficial wet sliding effect, in particular insofar as they cause the lubricant to accumulate on the surface of the goods and the liquor accumulates in the immediate vicinity of the lubricant and as a flowing liquor layer wet gliding of the goods is surprisingly much easier.
  • the effectiveness of the preparations (L), especially in the sub-fleet area, can be determined by measuring the Friction coefficients e.g. can be determined as follows: A first piece of fabric is attached to the inside floor stretched against a low, flat tub, fastened with a clamp at one end and with a lot of fleet covered, which corresponds to the usual fleet conditions; then a 200th g Weight with smooth, flat, rectangular bottom on which a second piece of the same Fabric is stretched and fastened, placed horizontally.
  • the overall effectiveness of the wet lubricant can be checked visually by checking the appropriately treated goods to determine chafing marks or marks on the creases (e.g. on a Staining).
  • Polyacrylamide (homopolymer) with a molecular weight M W of 2 ⁇ 10 6 .
  • wax dispersion (W1) 540.0 parts are obtained, which are added to 2451.0 parts of an aqueous solution of 3.0 parts of macrocopolyacrylamide (B11) in 2448.0 parts of water, at room temperature, with stirring. Now 6.0 parts of a 37% aqueous formaldehyde solution are added, then 3.0 parts of a 1.5% aqueous solution of 2-methyl-4-isothiazolin-3-one, which still has 1 , 75% Mg (NO 3 ) 2 , 0.85% MgCl 2 and 0.12% Cu (NO 3 ) 2 , is added as a microbicide and then unloaded. 3000.0 parts of an aqueous dispersion (L1) with a flow time (Erichsen, Ford Cup No. 4, ASTM-D 1200, 73/050) of 32 seconds (at 22 ° C.) are obtained.
  • a flow time Erichsen, Ford Cup No. 4, ASTM-D 1200, 73/050

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  • Textile Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Paints Or Removers (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Coloring (AREA)
EP98810558A 1998-06-18 1998-06-18 Wässrige Dispersionen, ihre Herstellung und Verwendung Withdrawn EP0965680A1 (de)

Priority Applications (14)

Application Number Priority Date Filing Date Title
EP98810558A EP0965680A1 (de) 1998-06-18 1998-06-18 Wässrige Dispersionen, ihre Herstellung und Verwendung
JP2000554917A JP4302892B2 (ja) 1998-06-18 1999-06-16 水性ディスパージョン、それらの製造および使用
ES99923804T ES2299247T3 (es) 1998-06-18 1999-06-16 Dispersiones acuosas, su produccion y uso.
BRPI9911275-2A BR9911275B1 (pt) 1998-06-18 1999-06-16 dispersÕes aquosas, sua produÇço e uso.
TR2000/03744T TR200003744T2 (tr) 1998-06-18 1999-06-16 Sulu dispersiyonlar, bu dispersiyonların üretimi ve kullanımı
AT99923804T ATE385270T1 (de) 1998-06-18 1999-06-16 Wässrige dispersionen, ihre herstellung und verwendung
PT99923804T PT1090179E (pt) 1998-06-18 1999-06-16 Dispersões aquosas, sua produção e uso
PCT/IB1999/001119 WO1999066118A1 (en) 1998-06-18 1999-06-16 Aqueous dispersions, their production and use
US09/720,065 US6736865B1 (en) 1998-06-18 1999-06-16 Aqueous dispersions, their production and use
IDW20002633A ID26638A (id) 1998-06-18 1999-06-16 Dispersi-dispersi yang mengandung air, produksi dan penggunaannya
DE69938079T DE69938079T2 (de) 1998-06-18 1999-06-16 Wässrige dispersionen, ihre herstellung und verwendung
EP99923804A EP1090179B1 (en) 1998-06-18 1999-06-16 Aqueous dispersions, their production and use
ZA200007035A ZA200007035B (en) 1998-06-18 2000-11-29 Aqueous dispersions, their production and use.
HK01105840A HK1035218A1 (en) 1998-06-18 2001-08-20 Aqueous dispersions, their production and use

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP98810558A EP0965680A1 (de) 1998-06-18 1998-06-18 Wässrige Dispersionen, ihre Herstellung und Verwendung

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EP99923804A Expired - Lifetime EP1090179B1 (en) 1998-06-18 1999-06-16 Aqueous dispersions, their production and use

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EP (2) EP0965680A1 (pt)
JP (1) JP4302892B2 (pt)
AT (1) ATE385270T1 (pt)
BR (1) BR9911275B1 (pt)
DE (1) DE69938079T2 (pt)
ES (1) ES2299247T3 (pt)
HK (1) HK1035218A1 (pt)
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1331302A1 (de) * 2002-01-28 2003-07-30 Dr. Th. Böhme KG Chem. Fabrik GmbH & Co. Faltenverhinderungsmittel
WO2008058593A1 (de) * 2006-11-14 2008-05-22 Clariant Finance (Bvi) Limited Verfahren zur kontinuierlichen herstellung von dispersionen in einem wirbelkammerreaktor
WO2008058592A1 (de) * 2006-11-14 2008-05-22 Clariant Finance (Bvi) Limited Verfahren zur kontinuierlichen herstellung von dispersionen in mikrostrukturierten apparaten

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Publication number Priority date Publication date Assignee Title
US20070155884A1 (en) * 2004-11-12 2007-07-05 Basell Poliolefine Italia S.R.L. Filled olefin polymer compositions having improved mechanical properties and scratch resistance
FR2879630B1 (fr) * 2004-12-22 2007-02-23 Emz Trek Nouvelle composition d'encollage de fils textiles

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GB2159844A (en) * 1984-06-08 1985-12-11 Sandoz Ltd Wax-containing dispersions for finishing textiles
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GB993794A (en) * 1961-02-13 1965-06-02 Rohm & Haas Wax compositions
NL6701483A (pt) * 1967-01-31 1967-04-25
DE2420971A1 (de) * 1973-04-30 1974-11-07 Du Pont Aethylencopolymerdispersion als wasserabweisender ueberzug
DE3334575A1 (de) * 1982-10-04 1984-04-05 Sandoz-Patent-GmbH, 7850 Lörrach Waessrige wachsdispersionen, deren herstellung und verwendung
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US4767669A (en) * 1987-04-21 1988-08-30 Burlington Industries, Inc. Melt size compositions containing surfactants
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1331302A1 (de) * 2002-01-28 2003-07-30 Dr. Th. Böhme KG Chem. Fabrik GmbH & Co. Faltenverhinderungsmittel
WO2008058593A1 (de) * 2006-11-14 2008-05-22 Clariant Finance (Bvi) Limited Verfahren zur kontinuierlichen herstellung von dispersionen in einem wirbelkammerreaktor
WO2008058592A1 (de) * 2006-11-14 2008-05-22 Clariant Finance (Bvi) Limited Verfahren zur kontinuierlichen herstellung von dispersionen in mikrostrukturierten apparaten

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EP1090179A1 (en) 2001-04-11
DE69938079D1 (de) 2008-03-20
DE69938079T2 (de) 2009-01-29
ID26638A (id) 2001-01-25
ES2299247T3 (es) 2008-05-16
BR9911275A (pt) 2001-03-13
PT1090179E (pt) 2008-02-28
ATE385270T1 (de) 2008-02-15
WO1999066118A1 (en) 1999-12-23
JP2002518549A (ja) 2002-06-25
ZA200007035B (en) 2001-11-29
US6736865B1 (en) 2004-05-18
JP4302892B2 (ja) 2009-07-29
HK1035218A1 (en) 2001-11-16
EP1090179B1 (en) 2008-01-30
TR200003744T2 (tr) 2001-04-20
BR9911275B1 (pt) 2008-11-18

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