Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/673—Inorganic compounds
  • D06P1/67333—Salts or hydroxides
  • D06P1/6735—Salts or hydroxides of alkaline or alkaline-earth metals with anions different from those provided for in D06P1/67341
• • 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
  • D06P1/62—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 low-molecular-weight organic compounds with sulfate, sulfonate, sulfenic or sulfinic groups
• • 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
  • D06P1/64—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 low-molecular-weight organic compounds without sulfate or sulfonate groups
  • D06P1/642—Compounds containing nitrogen
  • D06P1/645—Aliphatic, araliphatic or cycloaliphatic compounds containing amino groups
• • 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
  • D06P1/653—Nitrogen-free carboxylic acids or their salts
  • D06P1/6533—Aliphatic, araliphatic or cycloaliphatic
• • 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
  • D06P1/673—Inorganic compounds
  • D06P1/67333—Salts or hydroxides
  • D06P1/67341—Salts or hydroxides of elements different from the alkaline or alkaline-earth metals or with anions containing those elements
• • 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
  • D06P5/15—Locally discharging the dyes
• • 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
  • D06P5/15—Locally discharging the dyes
  • D06P5/151—Locally discharging the dyes with acids or bases
• • 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
  • D06P5/15—Locally discharging the dyes
  • D06P5/158—Locally discharging the dyes with other compounds

Definitions

• This invention relates to the printing of fabrics and improvements therein.
• An important variant of textile printing is the process of discharge printing whereby a suitably dyed fabric is printed with a suitable printing ink which contains a chemical (or chemicals) capable of destroying the chromogenic system of the dyes under appropriate conditions, usually heating or steaming.
• a chemical (or chemicals) capable of destroying the chromogenic system of the dyes under appropriate conditions usually heating or steaming.
• This destruction of the ground colour of the fabric provides a coloured fabric with a design of substantially uncoloured material.
• the printing ink additionally may contain colouring materials which are resistant to the chromogen destroying reactions of discharging and also a means of fixing such colouring materials to the fabric under the physical conditions of discharging.
• Such so-called "illuminated" discharge prints generally are produced using vat dyes or resin bonded pigments as colouring materials.
• colouring materials is used to indicate a pigment or a dyestuff which will give a coloured effect, and the term is used to include both black and white as well as spectral colours.
• the chemicals used substantially to destroy the colouring materials in discharge printing processes will hereinafter be referred to as “discharging agents”.
• Discharge printing processes have been described in which a dyed fabric, usually cotton or some other cellulosic or substantially cellulosic material, is printed with a colouring material containing a discharging agent and dried. At this stage, little or no discharge effect may be seen. The dried print is then steamed at, typically, 102-104°C for several minutes, during which time the discharge reactions proceed. The fabric is then washed off, dried and processed further if required.
• EP-A-0036252 describes a process of decorating dyed fabric which is printed with a first colouring material containing a discharging agent and then dried to fix it to the fabric. A second colouring material is also applied, before or after the first. The first prevents some of the dye in the second from becoming fixed to the fabric. It is necessary to wash off the fabric to remove such dye as has been prevented from fixing, before the effects of the process are visible.
• EP-A-0416888 describes a process of decorating a dyed fabric where the fabric is printed with a colouring material which contains a discharging agent and also an unusually high concentration of humectant.
• the fabric is heated between impermeable layers at a high enough temperature to produce localised superheated steam from the water in the printing ink to promote the discharge reactions.
• This procedure has the advantage that the heat treatment is shorter and produces the discharge design within a short time of printing, thus allowing early inspection of the print quality.
• Printing ink formulations can also be devised for this procedure which permit the final washing off stage to be optional.
• a further discharge printing process is where the dyed fabric is printed with a specially formulated discharge ink containing pigments and pigment bonding agents, urea or a substituted urea and a discharging agent formulated so that the discharge effect is produced during a simple drying and baking operation designed to fix the pigment.
• Typical conditions for this kind of procedure may be provided by an oven operating at 190-200°C with a treatment time of 1-2 minutes. This procedure requires no steaming or washing off and is particularly advantageous for printing garments or garment panels, so-called "unit printing", as distinct from the printing of continuous web fabric which normally utilises any of the other above described procedures.
• the zinc salt is particularly useful, especially when illuminated prints are to be produced since zinc formaldehyde-sulphoxylate has an acid reaction favourable to the curing of the acrylic binding agents generally used in such a process. Furthermore, reduction under mildly acid conditions generally favours the production of more weakly coloured degradation products from the discharge reactions than is obtained when using the alkaline sodium or calcium salts.
• Formaldehyde is a known carcinogen and irritant and accordingly, fabric bearing such a residue may represent a health hazard or provide a skin sensitisation problem to those coming into contact with the fabric, such as those who work with the fabric to make garments or the first wearer of a garment made from the fabric.
• thiourea dioxide which re-arranges under alkaline conditions to form formamidine sulphinic acid. Because of their isomeric relationship the descriptions thiourea dioxide and formamidine sulphinic acid are generally regarded as being synonymous and the term thiourea dioxide in the following may be regarded as embracing formamidine sulphinic acid unless otherwise stated. This, like zinc formaldehyde-sulphoxylate, breaks down during the discharge printing process to the highly reactive sulphoxylic acid, but neither contains nor produces any formaldehyde.
• thiourea dioxide has limited use in discharge printing.
• thiourea dioxide effectively only on processes involving steaming or in the presence of substantial amounts of non-volatile agents capable of acting as high temperature solvents or reaction media such as polyethylene glycols as described in the UK specifications 939515 and 1026236, as such conditions have, until now, been found necessary for the releasing of the active reaction products.
• a process of decorating dyed fabrics comprising the steps of: applying a printing paste to desired image areas to form a design in the fabric, the printing paste containing at least one reagent capable of reacting with the dye in the fabric at least substantially to destroy its colour, the or one of the reagents being thiourea dioxide, and subjecting the applied paste to a treatment process for fixing the design in the fabric, characterised in that the printing paste also contains at least one finely dispersed calcium, magnesium or zinc hydroxide or components which, under the conditions of the treatment process, form such finely dispersed calcium, magnesium or zinc hydroxide and an amine.
• the finely dispersed hydroxide may be produced in situ in the printing paste from a mixture of an amine or ammonia, together with at least one water soluble calcium, magnesium or zinc salt.
• the relative proportions are preferably stoichiometric or, preferably, with an excess of amine or ammonia, though too great an excess should be avoided as unreacted amine or ammonia can lead to binder curing problems.
• it may be produced by hydration of finely dispersed oxide in the presence of an alkali, for example an aliphatic amine or ammonia.
• finely dispersed hydroxide in the printing paste as such, since this avoids the presence of alkaline electrolyte in the printing paste and reduces the risk of problems arising if electrolyte sensitive pigments, binders or thickeners are present in the paste.
• the amount of metal salt or other source of finely dispersed hydroxide should be sufficient to give adequate discharge properties to the print paste.
• the amount is sufficient to give a concentration in the print paste of at least 0.1 moles/litre, and a concentration of around 0.3 moles/litre of hydroxide has been found to give good results, with increased concentrations showing no material improvement.
• the discharge printing paste used in carrying out the invention which contains, in addition to thiourea dioxide, the finely dispersed hydroxide, as such or produced in situ , can be used for the effective production of discharge effects under dry heat conditions as well as in procedures requiring steam treatment.
• Preferred amines for use in the printing paste together with a calcium, magnesium or zinc salt are aliphatic amines such as mono-ethanolamine, di-ethanolamine, tri-ethanolamine, mono-isopropanolamine and di-isopropanolamine. Monoethanolamine is most preferred as this is found to yield discharge products which are less coloured.
• Any water soluble magnesium, calcium or zinc salt may be used such as a chloride, sulphate, nitrate or acetate.
• Acetates are generally preferred due to their weaker acid reaction and less deleterious effect than the other salts on thickening agents normally present to provide an ink of printable viscosity.
• hydroxide is produced in situ during the treatment process, it is automatically produced in very finely dispersed form. If, as is preferred, it is present as such in the printing paste, it is preferably of particle size ⁇ 7.5 ⁇ .
• Such finely dispersed hydroxides may be added as an anhydrous powder or pre-dispersed in water when formulating the printing paste for a given fabric decorating run.
• the printing paste contains agents for assisting the colour destroying reaction of the fabric dye and discharging agent, such as acids, alkalis, reduction catalysts and the like.
• the printing paste may contain colouring materials which are chemically stable to the discharging agent(s), and which are capable of being fixed to the fabric during the process of the present invention.
• these colouring materials are dispersed pigments.
• agents may be present such as resin binders which are capable of polymerising to bind the colouring materials to the fabric.
• Acrylic or polyurethane resin emulsions have been found to be most suitable for this purpose. Catalysts which promote the curing of the binder or binders may also be present in the printing paste.
• discharge printed or decolorised image areas on the fabric may be overprinted with colouring materials to produce a design in a second printing step.
• agents may be present in the discharge inks produced in accordance with the present invention to assist the printing process or enhance the properties of the printed fabrics.
• examples include thickening agents, softening agents, flame proofing additives, wetting agents, and cross-linking agents.
• the thickening agents may be derived from polyacrylic acid, polyurethanes, emulsified white spirit, materials derived from cellulose, guar gums, other carbohydrates or any other suitable material.
• Binding agents may be selected from the wide variety of binding agents available for the production of pigment prints on textiles as is the case also with regard to flame proofing or softening agents.
• Cross-linking agents include the condensation products of formaldehyde with urea, urea derivatives, melamine or triazones, as well as glyoxal and 2,2'-dimethoxy ethanol.
• a printing paste is prepared containing (parts by weight):
• Alcoprint is a Registered Trade Mark.
• a knitted garment panel dyed to a red shade using Remazol (Registered Trade Mark) Brilliant Red 3B (ex DyStar UK Ltd) is screen printed with a design using the above ink and then passed down a drying/curing oven operating at 200°C with a total heating time of 2 minutes.
• the red shade is destroyed to leave a bright blue decoration which is fast to washing. If the mono-ethanolamine or the zinc acetate is omitted from the above recipe, the red shade is very poorly discharged and the decoration is of a dull and unsatisfactory shade.
• the formaldehyde content is found to be ⁇ 100 parts per million.
• a printing paste is prepared containing the following in parts by weight:
• Imperon is a Registered Trade Mark.
• a knitted garment panel dyed to a red shade using Remazol Brilliant Red 3B (DyStar UK Ltd) is screen printed with a design using the above ink and then passed down a drying/curing oven operating at 195°C with a total heating time of 150 seconds.
• the red shade is destroyed to leave a bright yellow decoration which is fast to washing. If the zinc hydroxide is omitted from the above recipe, the red shade is very poorly discharged.

Landscapes

• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Coloring (AREA)
• Chemical Or Physical Treatment Of Fibers (AREA)
• Decoration Of Textiles (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)

Applications Claiming Priority (2)

Publications (3)

Family

ID=10789928

Family Applications (1)

Country Status (4)

Cited By (2)

Citations (6)

Family Cites Families (4)

• 1996
  • 1996-03-06 GB GB9604738A patent/GB2310867B/en not_active Expired - Lifetime
• 1997
  • 1997-03-06 DE DE69725371T patent/DE69725371T2/de not_active Expired - Lifetime
  • 1997-03-06 EP EP97301520A patent/EP0799930B1/de not_active Expired - Lifetime
  • 1997-03-06 AT AT97301520T patent/ATE251688T1/de not_active IP Right Cessation

Patent Citations (6)

Non-Patent Citations (2)

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