WO1998055327A1 - Impression sur un cadre resistant a la chaleur - Google Patents

Impression sur un cadre resistant a la chaleur Download PDF

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Publication number
WO1998055327A1
WO1998055327A1 PCT/GB1998/001647 GB9801647W WO9855327A1 WO 1998055327 A1 WO1998055327 A1 WO 1998055327A1 GB 9801647 W GB9801647 W GB 9801647W WO 9855327 A1 WO9855327 A1 WO 9855327A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
screen printing
ceramic
printing ink
substrate
Prior art date
Application number
PCT/GB1998/001647
Other languages
English (en)
Inventor
Stephen Hoskins
David Fortune
Richard Anderton
Original Assignee
University Of The West Of England, Bristol
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 University Of The West Of England, Bristol filed Critical University Of The West Of England, Bristol
Priority to AU77815/98A priority Critical patent/AU7781598A/en
Priority to GB9928796A priority patent/GB2340791B/en
Publication of WO1998055327A1 publication Critical patent/WO1998055327A1/fr

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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
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/12—Transfer pictures or the like, e.g. decalcomanias
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • B41M1/12—Stencil printing; Silk-screen printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • B41M1/26—Printing on other surfaces than ordinary paper
    • B41M1/34—Printing on other surfaces than ordinary paper on glass or ceramic surfaces

Definitions

  • This invention relates to a water miscible screen printing medium and enamel composition for use in the decoration of a heat-resisting base, such as a ceramic material (pottery), glass or vitreous enamels.
  • a heat-resisting base such as a ceramic material (pottery), glass or vitreous enamels.
  • This invention also relates to a method of making the medium and enamel composition, to a water-slide decal which is used to transfer a printed image (the image having been printed using the medium/enamel composition of the invention) onto the said heat-resisting base and to a process for decorating a heat-resisting base using the water-slide decal of the invention.
  • ceramic enamel means a composition comprising a pigment and a fluxing agent for the pigment.
  • the fluxing agent may be a glass frit which melts at high temperatures, but may be any substance which fuses the pigment to the heat- resistant base.
  • Typical ceramic enamels are available from ceramic manufacturers, e.g. Cookson Matthey, Degussa and Haraeus .
  • the ceramic enamel comprising pigment and frit is normally available in a particulate form, as obtained by grinding to form a coloured powder, the particles of which are normally smaller than about 50 ⁇ m.
  • Ceramic enamels are produced to very exacting requirements and must be able to withstand high firing temperatures and be resistant to chemical attack. There are therefore only a small number of pigment systems available for ceramic enamels; these include spinels (MgAl 2 0 4 ) and cadmium sulphur selenides (communally reds and yellows) , and the more recently developed zirconium encapsulated pigments where the pigment is protected by a zircon shell .
  • the colour of enamels depends on its composition and is usually determined by the metal ion in the pigment.
  • Frits are usually lead borosilicate glasses with a melting point of between 700 and 1200 °C depending on the application temperature. Additives to the frit control its properties for different applications. For example, aluminium is added to improve resistance, while alkali metals are added to lower the melting point. Lead-free systems have been developed recently due to concerns about lead leaching from ceramic ware and lead intake by workers in the ceramics industry.
  • covercoat layer is then printed over the image.
  • the covercoat layer is based on polymeric methacrylate resins dispersed in organic solvents (such as toluene, acetone, methylethylketone) with additives such as plasticisers (phthalates chlorinated diphenyls and polyphenols) .
  • the decal is releasable from the stock by the dissolution of an underlying, starch based water-soluble gum layer or a similar carrier.
  • the decal is then applied to the surface of the ceramic or other article to be decorated. Residues of gum allow the resultant film to adhere to the ceramic surface and act as a lubricant to aid the positioning of the image.
  • the article is fired at a temperature, normally above about 750°C, at which the ceramic enamels in the image bond permanently to the ware .
  • organic media are mixed with ceramic enamel to give an ink suitable for screenprinting.
  • the media dry to form a solid film from the liquid phase.
  • the nature of the drying process varies according to the physical and chemical processes involved. The most common drying method is by evaporation of the solvent. These media burn off without residue at an early stage during the firing, before the frit fluxes to the glaze.
  • These media are based on synthetic resins, including formaldehyde resins, polyvinyl acetate resins, polymethacrylate systems . The type of polymer used determines the use of solvents. Common solvents are aliphatic hydrocarbons (e.g.
  • aromatic hydrocarbons such as xylene and toluene
  • oxygenated compounds such as ethers, alcohols and ketones.
  • Other additives may also be present in the medium to control its physical properties. These may be plasticisers, dryers and retarders . In addition to the hazards associated with inhalation of the volatile solvents, they have been shown to give rise to contact dermatitis on prolonged exposure.
  • Water miscible ceramic printing inks for use in the decoration of ceramics are known, for example in hand decorated material, but these have not been considered suitable for use in mass-production processes for decorating ceramics using water-slide decals for use in screen printing. This is due to their water solubility leading to breakdown of the image when immersed in water in order to release the image and covercoat from the base paper.
  • water-based ceramic inks are known which are used for direct printing onto flat ware.
  • a water-proof, water miscible ceramic decal ink is now proposed.
  • a water miscible ceramic screenprinting ink comprising a ceramic enamel dispersed in an aqueous screen printing medium, and which additionally comprises a waterproofing agent .
  • the water-proofing agent is included in the ink to permit it to be used in the preparation of water- slide decals, by rendering the image insoluble in water.
  • the ceramic ink of the invention will contain approximately 55% by weight of the ceramic enamel. This amount is variable, for example by as much as 15%, depending on the ceramic enamel used.
  • the aqueous screen printing medium in which the ceramic enamel is dispersed is preferably polymeric and a typical example is a medium based on polyethylacrylate or a water miscible emulsion of polymethylmethacrylate .
  • Various conventional screen printing additives may be present in the medium.
  • the amount of screen printing medium present varies according to the physical properties of the ceramic enamel used but is typically greater than 20% by weight. Typically the medium present may be approximately 35% by weight of the ink, although more could be present depending on the particular circumstances .
  • the water-proofing agent is generally present in an amount of up to 10% by weight of the ink.
  • a preferred group of water-proofing agents which is an 80% modified polyfunctional aziridine. The preferred amount of such a water-proofing agent is about 2% by weight of the ink.
  • the ceramic printing ink of the invention may comprise one or more of the following: a drier, a retarder and an extender.
  • a water miscible retarder may be present, typically in an amount of approximately 3% of the sum total weight of the mixed ink.
  • the retarder may be added to slow the drying time of the ink and thereby acts to retain the fluidity of the ink for screen printing.
  • the retarder may be replaced by water.
  • the water miscible screen printing ink composition of the invention may be prepared by the following steps :
  • step (b) mixing a water-proofing agent with the mixture obtained from step (a) .
  • the water-proofing agent is added as the final component, even when the other components mentioned above are present in the composition, as it shortens the shelf life of the ink and is therefore mixed shortly before printing commences.
  • a water miscible retarder may be mixed with the components, preferably at step (a) .
  • the screen Prior to printing, the screen is preferably washed with a mild alkaline solution in order to prevent crosslinking and the medium drying into the screen, thus prolonging the time available for printing.
  • Screens for printing are made in the conventional manner for water based screenprinting in the paper and board industry.
  • a typical example is a 150t monofilament polyester mesh stretched to 14 Newtons coated with Folex dc200 direct screen emulsion.
  • the ink composition of this invention in combination with screens such as these can be printed and has been tested on a range of screen printing machines including hand benches, semi automatics and cylinder presses.
  • the ink composition of the invention may be employed in the preparation of improved transfers for use in the decoration of a heat-resisting base.
  • Such transfers comprise a substrate and the printed image separated from each other by a release layer, such as a gum, which is capable of releasing the printed image from the substrate on soaking of the transfer in water and which additionally serves as an adhesive for adhering the printed image to the heat-resisting base.
  • the substrate is a paper.
  • the transfer comprises a water- insoluble covercoat which acts as a support for the printed image. The covercoat may be located or positioned on the side of the image away from the substrate, or may be located on the side of the image against the substrate, albeit separated from the substrate by the release layer.
  • covercoat has always been an outer layer (hence the term covercoat) so that, when the image and associated cover layer are released from the substrate and applied to an article to be decorated, the cover layer is outermost. This was believed necessary to ensure that, on firing, the decomposition products of the covercoat would not interfere with the printed image. It has now been discovered, however, that when the printed image is one derived from a water miscible enamel composition of the invention, the covercoat may be located between the release layer and the image.
  • covercoat can be laid down on the substrate, by a printing process, for example, and the image then printed on top of the covercoat. This ensures that the water miscible ink does not interact with the release layer which is often a water-soluble gum.
  • the covercoat is based on cellulose acetate butyrate (CAB) . This may be dispersed in a mix of acetone and methylethylketone with diethylphthalate plasticiser.
  • the covercoat layer may be up to 50 ⁇ m thick and typically is of the order of lO ⁇ m thick.
  • the improved transfers of this invention may be used in a process for decorating a heat-resisting base.
  • the transfer is soaked in water for a period sufficient to allow removal of the covercoat layer with the printed image from the substrate.
  • the image is subsequently located on the heat-resisting base with the covercoat located against the base and is fixed thereto on firing, leaving no discernible residue.
  • Firing typically takes place at a temperature in the range of 650-900°C. However, this may vary depending on the required application.
  • a transfer comprising a substrate and a printed image which are separated from each other by a release layer, which release layer is capable of releasing the printed image from the substrate on soaking of the transfer in water and which additionally serves as an adhesive for adhering the printed image to a heat resisting base, wherein the transfer further comprises a water-insoluble covercoat which is located on the side of the image against the substrate, albeit separated from the substrate by the release layer.
  • a kit for use in preparing a water-slide decal comprising: a decal paper, one surface of which is provided with a release layer; a water-proofing agent for addition to a water- miscible screen printing ink, and which is capable of rendering the dried image formed from the ink water- insoluble.
  • the kit may additionally comprise a retarder to slow drying of the ink and/or a supply of a suitable screen printing medium.
  • a suitable covercoat for example a cellulose acetate butyrate (CAB) layer may be provided over the release layer of the decal paper to a depth of, for example, lO ⁇ m.
  • CAB cellulose acetate butyrate
  • the kit is used in a method of preparing a water- slide decal.
  • the water-proofing agent is incorporated in the water-miscible screen printing ink containing the ceramic enamel in an amount suitable to render a dried image from the ink water-insoluble .
  • the ink (or a plurality of inks) are screen printed onto the surface of the decal paper provided with the release layer.
  • the resultant decal may then be used in the normal way whereby the printed image is released from the decal paper and applied to the surface of a heat-resisting base, prior to firing in the traditional way.
  • a water-insoluble covercoat is provided over the release layer to act as a support for an image to be printed thereon.
  • the decal paper may be a so-called Duplex or Simplex paper.
  • the release layer may be a conventional gum.
  • the kit may also include suitable instructions for use .
  • EXAMPLE The following trials were conducted on the water miscible medium developed for ceramic transfers . Press facilities included a cylinder press (Sias) , a semi automatic (Svecia) , and hand bench trials. A four colour design was chosen and was prepared in Folex DC- 200 waterproof emulsion on 150 mesh polyester screens. The composition used was as follows :
  • Water-proof water miscible medium 20% Waterproofing agent 10%
  • a retarder was added (in an amount of up to 3% of the sum total of the composition) .
  • the ceramic enamels selected were a commercial ceramic four colour printing set: (CMYK) yellow, cyan, magenta and black, as supplied by Heraeus .
  • the inks were prepared by mixing these ceramic enamels with the medium at a ratio of 3.5:1 (70%: 20%) .
  • the ceramic enamel :medium ratio was progressively reduced to 2.5:1, at which point the ceramic enamel were judged to have an acceptable printing viscosity.
  • To each of these inks was added 3% of the retarder, and the mixture was then triple roll-milled. Instead of triple roll- milling, Hobart mixing could be used.
  • the substrate chosen was a commercially available transfer paper, known as Ceramicol, which carried a lO ⁇ m coating of cellulose acetate butyrate (CAB) ; the applicants have applied transfers prepared on this substrate directly after printing the inks, i.e., without the use of a covercoat on top of the transfers, in accordance with the claimed invention.
  • CAB cellulose acetate butyrate
  • the inks were printed in the usual order: yellow, cyan, magenta, black, and racked between each colour.
  • the screen Prior to printing, the screen was washed thoroughly with an alkaline preparation (the commercial cleaner Mr Muscle which is ammonia-based) . The washing was important, as traces of acid still present in the emulsion after engraving can cause the ink to crosslink and dry in the mesh.
  • Printing speeds were relatively high at approximately 200 per hour. All washing up between colours was undertaken with water. After printing each colour the sheets were racked at room temperature; they were sufficiently dry to be handled and printed with the next colour within about 15 minutes compared with several drying days necessary to print a conventional solvent based four colour set.
  • Tunnel Dryer with a belt speed the equivalent of that required to print at 1200 sheets per hour (with the appropriate 80mm gap between sheets) .

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Printing Methods (AREA)
  • Decoration By Transfer Pictures (AREA)

Abstract

On décrit une encre céramique pour sérigraphie miscible dans l'eau, qui comprend un émail pour céramique dispersé dans un milieu aqueux d'impression sérigraphique, ainsi qu'un agent d'étanchéité. On décrit également un procédé de préparation de ladite encre, un procédé de transfert réalisable avec ladite encre et un procédé de décoration d'un cadre résistant à la chaleur.
PCT/GB1998/001647 1997-06-04 1998-06-04 Impression sur un cadre resistant a la chaleur WO1998055327A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU77815/98A AU7781598A (en) 1997-06-04 1998-06-04 Printing onto a heat-resistant base
GB9928796A GB2340791B (en) 1997-06-04 1998-06-04 Printing onto a heat-resistant base

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9711556.2 1997-06-04
GBGB9711556.2A GB9711556D0 (en) 1997-06-04 1997-06-04 Printing onto a heat-resistant base

Publications (1)

Publication Number Publication Date
WO1998055327A1 true WO1998055327A1 (fr) 1998-12-10

Family

ID=10813560

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1998/001647 WO1998055327A1 (fr) 1997-06-04 1998-06-04 Impression sur un cadre resistant a la chaleur

Country Status (3)

Country Link
AU (1) AU7781598A (fr)
GB (1) GB9711556D0 (fr)
WO (1) WO1998055327A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2522525A1 (fr) * 2011-05-10 2012-11-14 Vitro Cristalglass, S.L. Procédé d'impression en sérigraphie sur une plate de verre et plaque de verre ainsi obtenue

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0539924A1 (fr) * 1991-10-29 1993-05-05 Manfred Neuberger Procédé et dispositif pour la fabrication des feuilles de transfert pour l'application des images, d'écriture et des dessins par cuisson sur des objets en céramiques
DE19533189A1 (de) * 1995-09-08 1997-03-13 Leipold Xaver F Gmbh & Co Kg Siebdruckmedium auf Wasserbasis zur Herstellung von insbesondere auf Glas oder Keramik einbrennbaren Abziehbildern

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0539924A1 (fr) * 1991-10-29 1993-05-05 Manfred Neuberger Procédé et dispositif pour la fabrication des feuilles de transfert pour l'application des images, d'écriture et des dessins par cuisson sur des objets en céramiques
DE19533189A1 (de) * 1995-09-08 1997-03-13 Leipold Xaver F Gmbh & Co Kg Siebdruckmedium auf Wasserbasis zur Herstellung von insbesondere auf Glas oder Keramik einbrennbaren Abziehbildern

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2522525A1 (fr) * 2011-05-10 2012-11-14 Vitro Cristalglass, S.L. Procédé d'impression en sérigraphie sur une plate de verre et plaque de verre ainsi obtenue

Also Published As

Publication number Publication date
AU7781598A (en) 1998-12-21
GB9711556D0 (en) 1997-07-30

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