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WO1996035757A2 - Epaississement de pates d'impression - Google Patents

Epaississement de pates d'impression Download PDF

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Publication number
WO1996035757A2
WO1996035757A2 PCT/GB1996/000954 GB9600954W WO9635757A2 WO 1996035757 A2 WO1996035757 A2 WO 1996035757A2 GB 9600954 W GB9600954 W GB 9600954W WO 9635757 A2 WO9635757 A2 WO 9635757A2
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WO
WIPO (PCT)
Prior art keywords
monomer
polymer
paste
particle size
emulsion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/GB1996/000954
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English (en)
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WO1996035757A3 (fr
Inventor
Norman Stewart Batty
Neil Anthony Barrett
Neil Harris
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Ciba Specialty Chemicals Water Treatments Ltd
Original Assignee
Allied Colloids Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Allied Colloids Ltd filed Critical Allied Colloids Ltd
Priority to AU53427/96A priority Critical patent/AU5342796A/en
Publication of WO1996035757A2 publication Critical patent/WO1996035757A2/fr
Publication of WO1996035757A3 publication Critical patent/WO1996035757A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof

Definitions

  • a print paste is a blend of one or more dyes or pigments, an aqueous carrier, a thickening polymer for controlling the viscosity and rheology of the print paste, and various other components generally including binder and ammonia or other alkaline agent.
  • the polymeric thickener is included in order to impart to the paste viscosity and rheology appropriate for printing of the paste. Because the paste often has a significant electrolyte content (for instance due to incorporation of electrolyte with the pigment and/or due to the alkaline conditions in the paste) it is necessary to select polymers that will give adequate viscosity and rheology despite the electrolyte. In addition to giving the desired rheology and viscosity, it is also necessary that the polymeric thickener should promote, or at least not detract from, the colour printing properties of the print paste. For instance it is well established that some polymers which can give good rheology and viscosity properties result in the print having a rather weak colour. This is referred to as a low "colour yield". It is therefore necessary to select a polymer which is a good thickener in the electrolyte-containing print paste and which gives good colour yield.
  • One class of polymer which has proved particularly successful is formed from water soluble monomer or monomer blend including an ethylenically unsaturated carboxylic monomer and which is in cross-linked, particulate, form.
  • the particle size is small (typically of the order of 1 to 2 ⁇ m) .
  • the monomer or monomer blend is such that, when the particles are in neutralised or part-neutralised form in the aqueous alkaline print paste, the particles swell to provide microgel latex thickening.
  • Such polymers typically are cross-linked acrylic acid or acrylic acid-acrylamide polymers made by reverse phase polymerisation as an emulsion in a non-aqueous liquid.
  • the particles are generally supplied to the print paste manufacturer as a liquid dispersion in a hydrocarbon liquid or other non-aqueous continuous matrix.
  • hydrocarbon liquid or other non-aqueous continuous matrix examples are volatile hydrocarbons, high boiling and relatively non- volatile mineral oils, vegetable oils, fatty acid esters and polyalkylene oxides. These materials are inevitably carried into the print paste with the polymer particles and this can be undesirable. For instance hydrocarbon may evaporate into the atmosphere and print obtained from such print pastes may release hydrocarbon or other material into the environment, for instance during washing of the printed textile or other substrate.
  • the powder may itself be contaminated by residues of the hydrocarbon or other non-aqueous carrier. Because the powder necessarily is very fine, there can be dust inhalation, respiratory and other handling problems even if it is agglomerated. It is difficult to meter, pump and measure the powders for automatic make-up systems and the admixing of the powders into the print paste incurs the risk of the formation of lumps and gels with consequential blockage of filters or the screen, and streaky printing. It is known that microgel thickening depends at least in part upon interaction between adjacent particles and that normally viscosification will increase as the particle size decreases.
  • print-paste thickeners of various types.
  • One type is a cross-linked, reverse phase polymerised, particulate polymer having a size below 4 ⁇ m emulsified in oil and made by the same general technique as discussed above except that the aqueous monomer blend includes a small amount of an associative monomer which can have the formula ABR, where A is an allyl ether group, B is a polyethoxy linkage and R is a hydrophobic alkyl or other long hydrocarbon group.
  • Another type is an acidic polymer-in-water emulsion that includes the associative monomer groups.
  • This polymer is made by emulsion polymerisation of a water-insoluble monomer blend which includes ethylenically unsaturated carboxylic monomer such as acrylic acid or methacrylic acid, ethylenically unsaturated non-ionic, water insoluble, monomer such as ethyl acrylate, optionally a cross-linking agent, and the associative monomer.
  • ethylenically unsaturated carboxylic monomer such as acrylic acid or methacrylic acid
  • ethylenically unsaturated non-ionic water insoluble, monomer such as ethyl acrylate
  • a cross-linking agent such as ethyl acrylate
  • This type of polymer- in-water emulsion is frequently referred to as an "associative thickener" and it is known to be effective despite the presence of electrolyte.
  • Such thickeners made using the allyl ether monomer ABR are commercially available from Allied Colloids Limited under the trade name Rheovis for various purposes, such as viscosifying emulsion paints.
  • Rheovis for various purposes, such as viscosifying emulsion paints.
  • an aqueous print paste according to the invention is thickened by a neutralised product of an acidic polymer-in-water emulsion which is the emulsion polymer of a water-insoluble monomer blend consisting of, by weight, (a) 10 to 60% ethylenically unsaturated carboxylic acid
  • the invention also includes the use of a polymer for thickening an aqueous pigmented print paste in which the polymer is provided as the defined acidic polymer-in-water emulsion.
  • the invention also includes a method of making a print paste by blending aqueous carrier, pigment and polymer and alkali, in which the polymer is provided as the defined acidic polymer-in-water emulsion.
  • the average particle size of the acidic polymer-in- water emulsion in the invention is always above 200nm and should be as large as is necessary to obtain a high colour yield, for instance approximately as high as is obtainable with Alcoprint PTF, or higher. Generally it is at least 220nm or 250nm and frequently above 300nm.
  • the size should not be more than about lO ⁇ m because of the need to ensure that the swollen polymer particles in use do not lead to blockages during printing.
  • the z-average particle size of the acidic polymer emulsion is below l ⁇ m, preferably below 750nm.
  • a range of polymers that differ substantially only in particle size can be made using different emulsification conditions from an otherwise similar polymerisation mixture of monomer blend and initiator.
  • the performance of such polymers in any particular print paste depends on the particle size.
  • colour yield increases significantly, without any significant decrease in viscosification performance, as the particle size increases up to a threshold value. Further increase in the particle size above the threshold value gives little or no further increase in colour yield.
  • the particle size should preferably not only be above 200nm, preferably above 300nm, but should also be above the threshold value of the particle size.
  • the threshold value for this purpose is defined as the particle size at which the colour yield is at least 80%, and preferably at least 90%, of the optimum colour yield obtainable in that paste with that range of polymers.
  • polydispersity indicates the slope of the leading edge of the distribution curve, with the result that as the slope approaches the vertical (indicating a narrow particle size distribution) the polydispersity approaches zero.
  • polydispersity is below 0.2, most preferably below 0.1.
  • the acidic polymer-in-water emulsion is made by polymerising an emulsion of the water-insoluble monomer blend, with monomer (a) in the form of free acid, in conventional manner under conditions that will yield the desired particle size.
  • These conditions generally consist of conventional oil-in-water emulsion polymerisation conditions modified by selection of the emulsification method and the nature and the amount of emulsifier so as to give the desired particle size in the final polymer emulsion.
  • Suitable emulsifiers are surface-active materials for example non-ionic types such as ethoxylated nonyl phenols or ethoxylated alcohols and anionic types such as ethoxylated alcohol sulphates, ethoxylated nonyl phenol sulphates, ethoxylated alcohol phosphates, sodium alkyl sulphates or sulphonates.
  • non-ionic types such as ethoxylated nonyl phenols or ethoxylated alcohols
  • anionic types such as ethoxylated alcohol sulphates, ethoxylated nonyl phenol sulphates, ethoxylated alcohol phosphates, sodium alkyl sulphates or sulphonates.
  • the preferred types are the ethoxylated alcohol phosphates.
  • the alcohol may be saturated or unsaturated, C 12 -C 18 linear or branched aliphatic, cycloaliphatic or araliphat
  • ethoxylated aliphatic alcohol phosphate or other suitable emulsifier it is also necessary to select the amount so as to obtain the desired particle size. Generally it is in the range 1 to 5%, preferably 1 to 3%, based on the weight of monomers.
  • Perlankrol ESD 216479 3.75% Perlankrol ESD was used. This is an ethoxylated alcohol sulphate emulsifier. Both these systems seem to give very small particle size, below 175nm.
  • the ethylenically unsaturated carboxylic acid (a) can be, for example, methacrylic acid, acrylic acid, itaconic acid, maleic acid, or mixtures of these acids. Methacrylic acid is preferred.
  • the alkyl ester monomer (b) can be an alkyl ester of any suitable ethylenically unsaturated carboxylic acid such as methacrylic acid or, more usually, acrylic acid.
  • the alkyl group can be substituted but is usually unsubstituted.
  • Suitable esters are, for example, ethyl acrylate, methyl acrylate, butyl acrylate, 2-ethyl hexyl aer late, or mixtures of these. Ethyl acrylate is preferred.
  • the associative monomer (c) is optional but is preferably included. For instance it improves viscosity and rheology, especially in the presence of electrolyte. It can be any appropriate ethylenically unsaturated monomer that carries a polyethoxy chain terminated in the hydrophobic group of at least 8 carbon atoms.
  • the ethylenically unsaturated monomer can be, for instance, an associative acrylic or other carboxylic ester, such as described in U.S. 4,384,096, or an acrylamide derivative such as described in U.S. 4,423,199, or a vinyl ether such as described in JP-A-60-235815, but is preferably an allyl ether as described in EP-A-216479.
  • ABR (c) is preferably included and A can be a methallyl group but is preferably allyl, B is a polyethoxy chain and R is a hydrophobic aliphatic or aromatic group of at least 8 carbon atoms.
  • the polyethoxy group can be interrupted by propoxy groups but preferably consists solely of ethoxy groups. There must be at least two and generally at least five ethoxy groups. There can be up to, for instance, 100 but generally there are 10 to 20 ethoxy groups in the linking group B.
  • R is generally selected from alkyl, aralkyl, alkaryl, aryl and cycloalkyl and usually contains 8 to 30, preferably 10 to 24, carbon atoms.
  • R is alkyl, especially stearyl or other hydrocarbon residue of a fatty alcohol.
  • a preferred associative monomer (c) is the allyl ether of ethoxylated stearyl or other fatty alcohol with 5 to 30, preferably about 10 to 20, moles ethylene oxide.
  • the polyethylenically unsaturated cross-linking agent (d) is optional and can be any conventional polyfunctional cross-linking monomer, for example, diallyl phthalate, divinyl benzene, tetraallyl oxyethane, triallyla ine, trisacryloyl hexahydro-l,3,5-triazine, preferably diallyl phthalate.
  • the monomer blend can include other monomer (e) provided it does not interfere with the formation of the acidic insoluble monomer blend and the acidic polymer-in- water emulsion by emulsion polymerisation.
  • Such other monomer can include water-soluble monomer such as acrylamide but, if present at all, it is generally a water insoluble monomer such as styrene or a substituted styrene, (meth)acrylonitrile, vinyl acetate or other alkanoate or vinyl or vinylidene chloride or other halide.
  • the amount of any such insoluble monomer is usually less than the amount of alkyl ester (b) and usually monomer (e) is omitted but it can be present in an amount of up to, for instance, 20%.
  • the amount of monomer (a) is generally, by weight of total monomer, 10 to 50%, preferably 25 to 45% and most preferably from 30 to 40%.
  • the amount of monomer (b) must be such that, with the other monomers, the blend can be polymerised by oil-in- water polymerisation and is usually in the range 40 to 90%, preferably 45 to 75% and most preferably from 45 to 60%.
  • Polymer emulsions formed by copolymerising monomers (a) and (b) and optionally (d) , in the absence of (c) , are useful and can give improved colour yield provided they have the defined particle size. They can also give adequate viscosification and rheology properties.
  • the monomers include at least 2% by weight of monomer (c) .
  • the presence of monomer (c) in the polymer gives particular improvement with respect to colour yield and performance when the print paste has a relatively high electrolyte concentration.
  • the amount of the associative monomer (c) is in the range 2 to 40%, preferably 5 to 20%, with best results generally being obtained with about 10 or 15% by weight of the associative monomer, based on the weight of the monomer blend.
  • the polymer In order that optimum microgel thickening occurs it is desirable that the polymer should remain in swollen particulate form in the print paste and accordingly the monomer blend should be such that the particles do not dissolve fully in the print paste.
  • the particles will retain their particulate structure if the monomer blend contains sufficient water-insoluble monomer (b) , (c) and (e) relative to the amount of potentially soluble monomer (a) , especially when polymerisation is conducted under conditions that lead to very high molecular weight. It is therefore possible to perform the invention using a polymer which is not deliberately cross-linked and in which the amount of monomer (d) is therefore zero.
  • the monomer blend should include cross linking monomer (d) , generally in an amount of at least 0.01% and preferably at least 0.05% (500ppm) . It is usually unnecessary for the amount to be more than 2% and amounts of from 0.05 to 0.15 or 0.2% are generally preferred.
  • Emulsification of the monomer blend, and the emulsion polymerisation may be conducted in conventional manner except for the described modification of the emulsification and the particle size.
  • the acidic polymer-in-water emulsion should be sufficiently storage-stable that it does not significantly and deleteriously settle out upon storage prior to use. If the particle size is sufficiently small, for instance sufficiently below 500nm, the emulsifier used to assist in the formation of emulsion will usually be sufficient to ensure adequate storage stability. However if the emulsion is not sufficiently storage-stable, and particularly if the emulsion has a large particle size(for instance above 750nm) , it may be desirable to stabilise the emulsion.
  • an acid-stable stabiliser is added, such as guar gum.
  • the acidic polymer-in-water emulsion is acidic in the sense that the carboxylic groups are either wholly in the acidic form or are sufficiently in the acidic form that the emulsion has low viscosity and can easily be mixed in with the other components of the print paste.
  • the paste can contain one or more pigments and/or dyes, such as disperse dye or reactive dye, typically in an amount of 1 to 10%, together with alkali such as alkali- metal hydroxide and/or ammonia in an amount sufficient to provide a pH of at least 6.5, often at least 7.
  • the paste may also contain binder and other conventional additives.
  • the amount of polymer which is added to the paste is selected to give the desired viscosity and is typically in the range 0.5 to 5%, often around 1 to 2 or 3%, dry weight of polymer based on the total weight of the paste.
  • the paste can be used for printing textiles or other substrates by techniques such as rotary or flat bed screen printing.
  • the substrate can typically be upholstery, sheeting, carpeting or clothing.
  • the particle size measurements in the examples are z- average particle size measured with a Malvern System 4700 Photon Correlation Spectrometer, with a helium-neon laser at 628nm and a scattering angle of 90°, at 20.0°, with the viscosity set at 0.8900Cp and the refractive index (liquid) set at 1.3300. 10ml of deionised water that has been filtered through a 0.2 ⁇ filter is poured into a 20ml vial and approximately 0.03ml of the emulsion is added from a pipette. The vial is capped and shaken gently. It is then put into the cell compartment of the instrument. It is left for 10 minutes to equilibrate to temperature before being tested. If the track of the laser through the liquid appears fuzzy, the sample is removed and diluted further. All the samples have a slight iridescence when they are tested. If they appear optically clear they are too dilute and are not used.
  • the scattered light is measured at a series of time intervals and the z-average particle size and the polydispersity calculated in accordance with the instructions in the Series 4700 Instruction Manual, IM 040,
  • emulsion particles are substantially spherical, similar numerical values for average particle size should be obtainable by other techniques, especially other Photon Correlation Spectroscopy techniques, if the
  • Malvern System 4700 is not available. Additionally, proprietary standard emulsion latices are available (such as the "Nanosphere" polystyrene latices from Duke
  • Malvern System 4700 an appropriate indication of whether or not any particular emulsion has a z-average particle size above a chosen value of, for instance, 200, 220 or 250nm can be made by comparison with such a standard using any suitable measuring technique.
  • a pigment stock is made up from: 40.Og Imperon Blue KRR (Hoechst) 120.Og Alcoprint PBA 10.Og .880 Ammonia 750g Deionised Water
  • the viscosity is measured with a Brookfield RVT rotary viscometer, spindle #6, at lOrpm.
  • the syringe is reweighed to find the weight of thickener added.
  • a paste is made in the same way with a standard thickener (Alcoprint PTF) and is used as a comparison for all the test prints.
  • Alcoprint PTF a standard thickener
  • a piece of the 50/50 polyester-cotton fabric about 35x50cm is cut and laid flat on the table of a Zimmer MDF- 240 laboratory printing machine.
  • a screen with an open blotch area 25x40cm is carefully placed over the fabric so that all of the blotch area is over fabric.
  • a number 4 magnetic bar is put in the screen so that there is a space of l-2cm between the bar and the edge of the blotch area.
  • the magnet is moved so that it is under the bar and is then switched on at power 2.
  • the magnet is moved across the screen at speed 5 so that it pushes the paste across the blotch in front of it and all the printed areas are continuous, i.e., there are no spaces between the printed marks.
  • the magnet is switched off and the screen carefully lifted away from the fabric.
  • the fabric is dried in a Benz drier for 1 minute at 110°C.
  • a standard scale is prepared by making and printing pastes thickened with a standard, for instance Alcoprint PTF.
  • a paste with 4% (40g/l) Imperon Blue KRR is prepared as described above. Similar pastes are prepared with amounts of Imperon Blue KRR in the stock at 4g intervals (36,32 etc) instead of the 40g, down to zero. Water is added so that the total weight is the same in every case.
  • the print with 4% Imperon Blue KRR is then 100% colour depth and the others 90%, 80%, etc., respectively.
  • the colour yield is then assessed by comparison with samples on this scale and can be quoted as a percentage of the standard. Alternatively the colour yield can be expressed as a percentage of the best colour yield obtained by any of the test polymers.
  • An aqueous feed was made up by weighing 198.5g of deionised water and 3.0g of a phosphate ester of the reaction product of oleyl alcohol with 3 moles of ethylene oxide into a beaker and stirring.
  • a monomer feed was made up by stirring 79.4g of methacrylic acid, lOOg of ethyl acrylate, 19.9g of the allyl ether of the reaction product of stearyl alcohol with
  • the aqueous feed was stirred with a high shear mixer and the monomer feed was poured slowly into it so that a stable monomer emulsion was formed.
  • the z-average particle size was measured as 186nm and the polydispersity was .029.
  • a printing paste was made up with 2.41g of dry polymer per lOOg of paste. It was a smooth paste with a viscosity of 20100CP.
  • Example 2 (Comparative) An emulsion polymer was made in exactly the same way as in Example 1, except that the emulsifier was sodium lauryl sulphate instead of the phosphate ester of the reaction product of oleyl alcohol with 3 moles of ethylene oxide. The dry weight of the product was 31.91%.
  • the z-average particle size of the polymer emulsion was found to be 130nm and the polydispersity was 0.089.
  • a printing paste was made with 1.71g of dry polymer per lOOg of paste. It was a smooth paste with a viscosity Of 19600CP.
  • a polymer emulsion was prepared as described above in Example 1 but the monomer solution was made with
  • the polymer emulsion obtained was found to be 30.03% active.
  • the z-average particle size was 252nm and the polydispersity was 0.062.
  • a printing paste was made with 1.72g of dry polymer per lOOg of paste. It was a smooth paste with a viscosity of 20700cP.
  • a polymer emulsion was prepared as described above in Example 3 but the reaction was carried out at 90°C instead of at 85°C.
  • the polymer emulsion was found to be 29.97% active.
  • the z-average particle size was 203nm and the polydispersity was 0.060.
  • a printing paste was made with 1.59g of dry polymer per lOOg of paste. It was a smooth paste with a viscosity of 19400cP.
  • a printing paste was made up as described below with Rheovis CRX (Allied Colloids) , a commercial associative polymer emulsion thickener (3.03% w/w of the emulsion). The viscosity was 19900cP. The print made as described below. The depth of colour was poor and was estimated to be only 50% of that of the standard.
  • the z-average particle size of the Rheovis CRX was found to be 85nm and its polydispersity was 0.227.
  • Example 6 (Comparative) A printing paste was made up as described below with Primal TT615 (Rohm and Haas) , a commercial associative polymer emulsion thickener. 1.87%w/w of emulsion was used. The viscosity was 21000cP. It was printed as described below. The colour yield was poor and was estimated to be only 55% of the standard.
  • the z-average particle size of the emulsion thickener was found to be 164nm and the polydispersity was 0.073.
  • Emulsion polymers prepared by the method of Example 1 but using various stabilising emulsifiers to achieve a range of particle sizes were tested as pigment print thickeners. Colour yield was compared to a standard using Alcoprint PTF.
  • a print paste was formulated as follows: 3515g of water was measured out and 300g of emulsion added with low speed stirring. 20.Og of antifoam (Burst 100) was dispersed in the solution and then 15.Og of sodium hydroxide (flake) were added and stirring continued for 5 minutes to ensure dissolution. pH was checked at this point and found to be 6.90. Maintaining low speed stirring, further additions of 100.Og sodium carbonate, 1000.Og of urea and 50.Og Ludigol (sodium-m-nitrobenzene sulphonate) were made, followed by stirring under high shear for 10 minutes to ensure complete dissolution of these components. During this period the viscosity of the paste increased to a final value of 30dPaS (Haake VT-02 viscometer, spindle no.l, measured at 20°C) . The final pH of the paste was 8.90.
  • Remazol Black B 250.Og of Remazol Black B were added to the above paste followed by stirring for 5 mins. under low shear to ensure complete mixing of colour. The final paste viscosity was measured at 26dPaS.
  • the paste was printed on to 100% plain woven cotton fabric (HO.Og/m) and 100% plain woven staple viscose fabric (132.0g/m 2 ) on a Stork RD-DD machine through a 195 Nova Screen.
  • the printed fabric was dried at 140°C for 50 seconds.
  • Fixation of colour was effected by steaming the fabrics at 102°C for 8 minutes followed by washing off on a continuous 8 bath counterflow washing range utilising a cold (20°C) rinse with water only in the first bath, a hot wash (95°C +) with 2.0g/l Alcosperse AD in the 2nd bath and then sequential rinses with water only ranging from 80°C to 20°C in the remaining 6 baths.
  • the fabrics were then stentered dry at 105°C for 2 minutes.
  • a paste was formulated as follows: 4380g of water was measured out and 20.Og of antifoam (Burst 100) was added with low speed stirring. 250.Og of the emulsion was added to this solution followed by 350.Og of ammonia solution (0.880 SG) . Speed of stirring was increased and maintained at maximum for 5 minutes after which the paste viscosity was measured as lOOdPaS (Haake VT-02 viscometer, spindle no.l, measured at 20°C) . 50.Og of Terasil Blue XBGE liquid was added to the paste and stirred for 5 mins. at low speed to ensure complete mixing. Viscosity was the same at 100 dPaS.
  • the paste was printed on to a knitted polyester fabric (150.0g/m) on a Stork RD-DD machine through a 125 mesh penta screen.
  • the printed fabric was dried at 140°C for 50 seconds.
  • Fixation of colour was effected by steaming at 140°C for 45 minutes followed by a washing treatment in a winch machine consisting of a cold (20°C) rinse, a hot scour at 90°C in a solution containing 2g/l Sapolib DCR plus lg/1 caustic soda flake and subsequent cold rinsing until clear.
  • a winch machine consisting of a cold (20°C) rinse, a hot scour at 90°C in a solution containing 2g/l Sapolib DCR plus lg/1 caustic soda flake and subsequent cold rinsing until clear.
  • the fabric was stentered dry.
  • Example 1 is an excellent thickener for disperse dye printing of polyester.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Pâte d'impression aqueuse épaissie par un produit neutralisé d'une émulsion acide polymère dans eau présentant une taille de particules plus importante que la taille habituelle des particules d'émulsions polymère dans eau. La taille des particules est d'au moins 200 nm, de préférence supérieure à 250 nm. Cette taille accrue des particules se révèle, de façon surprenante, capable d'entraîner une production de couleur améliorée.
PCT/GB1996/000954 1995-04-24 1996-04-19 Epaississement de pates d'impression Ceased WO1996035757A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU53427/96A AU5342796A (en) 1995-04-24 1996-04-19 Thickening of print pastes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9508242.6 1995-04-24
GBGB9508242.6A GB9508242D0 (en) 1995-04-24 1995-04-24 Thickening of print pastes

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Publication Number Publication Date
WO1996035757A2 true WO1996035757A2 (fr) 1996-11-14
WO1996035757A3 WO1996035757A3 (fr) 1997-01-16

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GB (1) GB9508242D0 (fr)
WO (1) WO1996035757A2 (fr)
ZA (1) ZA963275B (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7153496B2 (en) 2002-01-18 2006-12-26 Noveon Ip Holdings Corp. Hair setting compositions, polymers and methods
US7288616B2 (en) * 2002-01-18 2007-10-30 Lubrizol Advanced Materials, Inc. Multi-purpose polymers, methods and compositions
WO2008028833A1 (fr) * 2006-09-06 2008-03-13 Huntsman Advanced Materials (Switzerland) Gmbh Pâte d'impression

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FR2227385B1 (fr) * 1973-04-27 1977-11-04 Ugine Kuhlmann
US4384096A (en) * 1979-08-27 1983-05-17 The Dow Chemical Company Liquid emulsion polymers useful as pH responsive thickeners for aqueous systems
AU612965B2 (en) * 1985-08-12 1991-07-25 Ciba Specialty Chemicals Water Treatments Limited Polymeric thickeners and their production
US4616074A (en) * 1985-10-01 1986-10-07 Alco Chemical Corporation Acrylic-methylene succinic ester emulsion copolymers for thickening aqueous systems
EP0333499B1 (fr) * 1988-03-18 1994-10-05 Ciba Specialty Chemicals Water Treatments Limited Procédés de polymérisation et produits obtenus à partir de ceux-ci

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7153496B2 (en) 2002-01-18 2006-12-26 Noveon Ip Holdings Corp. Hair setting compositions, polymers and methods
US7288616B2 (en) * 2002-01-18 2007-10-30 Lubrizol Advanced Materials, Inc. Multi-purpose polymers, methods and compositions
US7649047B2 (en) 2002-01-18 2010-01-19 Lubrizol Advanced Materials, Inc. Multi-purpose polymers, methods and compositions
WO2008028833A1 (fr) * 2006-09-06 2008-03-13 Huntsman Advanced Materials (Switzerland) Gmbh Pâte d'impression

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ZA963275B (en) 1997-04-24
WO1996035757A3 (fr) 1997-01-16
AU5342796A (en) 1996-11-29
GB9508242D0 (en) 1995-06-14

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