EP1358076A2 - Decalcomanie pour decorer des articles ceramiques ou en verre - Google Patents

Decalcomanie pour decorer des articles ceramiques ou en verre

Info

Publication number
EP1358076A2
EP1358076A2 EP01272000A EP01272000A EP1358076A2 EP 1358076 A2 EP1358076 A2 EP 1358076A2 EP 01272000 A EP01272000 A EP 01272000A EP 01272000 A EP01272000 A EP 01272000A EP 1358076 A2 EP1358076 A2 EP 1358076A2
Authority
EP
European Patent Office
Prior art keywords
decal transfer
polymers
aqueous composition
production
decal
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.)
Withdrawn
Application number
EP01272000A
Other languages
German (de)
English (en)
Inventor
Dario Chiavacci
Alan Nappa
Stefano Crespi
Giuseppe Li Bassi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lamberti SpA
Original Assignee
Lamberti SpA
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 Lamberti SpA filed Critical Lamberti SpA
Publication of EP1358076A2 publication Critical patent/EP1358076A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
    • B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
    • B44C1/17—Dry transfer
    • B44C1/1704—Decalcomanias provided with a particular decorative layer, e.g. specially adapted to allow the formation of a metallic or dyestuff layer on a substrate unsuitable for direct deposition
    • 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

Definitions

  • the object of the present invention is an aqueous composition useful for manufacturing the decal transfer used to decorate ceramic articles or glassware and to give them specific features of aesthetic and/or functional order.
  • composition of the present invention enables the elimination of the emission of volatile organic compounds during the manufacture of decal transfer.
  • decal transfer is referred to the film or sheet, possibly made of ceramic glaze, comprising an image or pattern which is to be transferred to a support.
  • a first step in which the image is formed on a support generally a sheet of paper, by means of any printing method.
  • This polymeric film is generally referred to as covercoat.
  • Conventional screen-printing is the printing method mainly used in the first step and consists of a series of superimposed impressions, one for each colour forming the final image.
  • continuous layers of special materials may also be applied, including fluxing agents to help the image fixation during the firing, or ceramic frits.
  • the surface of the paper sheet is treated with polysaccharide derivatives or with other water-soluble compounds.
  • the water passes through the paper dissolving the water-soluble layer, thus allowing the easy detachment of the covercoat bearing the decoration and the possible other layers.
  • heat release decal transfer which are more suitable to automated systems, the support sheet is coated with low melting polymers or with polymers exhibiting poor adhesion with the covercoat bearing the decoration: the covercoat is removed from the supporting paper by putting it in contact with a pre-heated pad of siliconic rubber of suited shape and dimension; then the pad itself transfers the decal transfer on to the object which is to be decorated, in the proper position.
  • decal transfer printed on a sheet of paper coated with polyethylene or with a siliconic polymer, or also on plastic films of the same low adhering polymers, this enabling its detachment by means of a simple machinery; a decal transfer wherein the image is printed directly on the covercoat film which is its sole support; a transfer sheet made up with a layer of particles of ceramic powders incorporated in a polymeric matrix or anyhow sufficiently bounded together to allow their detachment and handling without the covercoat layer.
  • the thickness of the layers comprising the image, the possible flux and/or the frit is generally comprised between 5 and 40 micron for common graphic image; between 40 and 100 micron for thick tri-dimensional patterns and between 30 and 300 micron when the layers will constitute a ceramic glaze coating.
  • the covercoat is from 15 to 70 micron thick.
  • the printing ink for the image and the possible layers of other materials are normally made of a solid ceramic portion dispersed in a liquid portion; the liquid portion carries the solids during printing and then it helps its consolidation .
  • the impression of the image on a ceramic surface or on glass requires that the solid portion is made by solid vitrifiable materials, or in other terms by materials which a following firing step at 600°- 1300° C will transform into ceramic. These materials are oxides, pigments, frits, glasses and other ceramic powders, all in form of solid particles having size in the range between 0.5 to100 micron.
  • the liquid medium essentially comprises: - a binding portion
  • the binding portion is normally constituted by polymers and copolymers (both terms briefly indicated as "polymers” in the present description) of acrylic and methacrylic acid esters, i.e. ethyl, n-butyl, i-butyl acrylate and methacrylate, or by cellulose acetate, cellulose butyrate or other cellulose derivatives.
  • the binding portion acts as a consolidating agent for the solid particles, avoiding their removal during the consecutive impressions; it must be easily removable during the firing, without interfering with the vitrification of the ceramic solid portion of the ink.
  • the binding portion is its flexibility, or in other terms its low glass transition temperature which can be further decreased by suitable plasticizing agents.
  • the solvent portion is normally constituted by aromatic solvents (i.e. white spirits and by compounds selected among glycol ethers, glycol ethers acetates, aliphatic hydro-carbons, aliphatic esters, turpentine and other terpene derivatives .
  • the solvent must possess a high volatility in order to be easily removed by evaporation after the application of the ink.
  • the removal of the solvent takes place at a temperature typically comprised between the ambient temperature and 60°C, and in any case at a temperature which does not damage the characteristics of the supporting sheet and of the binding polymers.
  • the covercoat is applied on the printed image.
  • the polymers which can be used to form the covercoat are particularly suitable.
  • the polymers and the copolymers of acrylic and methacrylic acid esters i.e. ethyl acrylate and methacrylate, n-butyl acrylate and methacrylate, iso-butyl acrylate and methacrylate
  • cellulose acetate, cellulose butyrate, nitro-cellulose and polyurethane are particularly suitable.
  • the covercoat must exhibit suitable mechanical characteristics; more specifically it must be as much flexible and plastic as to let the decal transfer adhere also on curved surface and resisting enough not to break when the decal transfer is detached from the supporting paper and laid on the ceramic ware.
  • covercoat must not be sticky, or the decal transfer piled for storage could stick to each other, and during firing, it must volatilize easily even at the lowest temperature, in order not to interfere with the layers lying below.
  • aromatic hydrocarbons aliphatic hydrocarbons, glycol ethers, glycol ethers acetate, acetone, 2-butanone, diacetone alcohol, methyl alcohol, ethyl alcohol, isopropyl alcohol , n-butyl alcohol, terpene derivatives such as dipentene, are the most suitable.
  • the solvent enables the application of the covercoat by means of a screen-printing manifold or roller machines.
  • the solvent must exhibit a high volatility in order to be easily removed by evaporation at a temperature typically comprised between the room temperature and 60°C.
  • the amount of solvent to be removed by evaporation ranges between 50 and 150 g/m 2 of decal transfer, if only the solvents in the ink and in the covercoat are considered.
  • a further consumption of solvent is to be added to this amount, due to the necessity of cleaning the printing machinery and particularly all the parts and the tools (screens, rollers and squeegees which become in touch with the printing media and the covercoat.
  • the chemical composition of the above mentioned solvents ( aromatics, iso- paraffins, glycol ethers, glycol ethers acetate, acetone, 2-butanone, diacetone alcohol, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, terpene derivatives such as dipentene), imply an eco-toxicolologic profile which exposes the workers, the environment and the social community to notable risks. Besides the question related to the toxicology and the occupational health, the problem of labour accidents caused by the flammability of the above mentioned solvents, their mixtures and their vapours must be carefully considered. In fact, in the view of the regulations regarding the storage, the transportation, the handling of chemical products, the main part of the solvents used in the production of decal transfer are flammable liquids.
  • aqueous composition for the production of decal transfer which replaces the normally used solvent-based compositions, comprising from 10 to 60% of one or more polymers selected in the group consisting of acrylic polymers, vinylic polymers, polyurethanes, alkydic polymers, polyesters, styrene-butadiene polymers.
  • polymers suitable for the realisation of the present invention are polymers of acrylic acid esters and of methacrylic acid esters, polyvinyl alcohol, copolymers of vinyl acetate, omopolymers and copolymers of vinylpirrolidinone, polyurethanes, styrene-butadiene resins, which can be used in the form of aqueous dispersions or solutions.
  • the aqueous compositions useful for the production of decal transfer are stabilised by adding one or more stabilising agents, preferably selected among surfactants and water-soluble polymers.
  • the preferred water-soluble polymers are polyvinyl alcohol, cellulose ethers and polyvinylpirrolidinone.
  • the particles dispersed in water have a size comprised between 0,01 micron and 40 micron, preferably between 0,1 and 6 micron.
  • the covercoat film formation takes place while water evaporates and the polymer particles combine together.
  • the aqueous compositions of the present invention may advantageously contain liquid water soluble substances able to solute the polymers.
  • Said substances are to be removed by evaporation after coalescence and must exhibit a sufficient volatility; they are typically carbitol glycol ethers, cellosolve glycol ethers, dipropyleneglycol monomethylether, ethyl lactate; their amount in the aqueous compositions ranges between 2 and 30 % by weight.
  • the aqueous compositions of the present invention may contain one or more other substances acting as de- foamers, biocides, dispersants or plasticiser agents.
  • the decal transfer produced by means of the aqueous compositions of the invention are supported by paper coated with polyesters or siliconic polymers.
  • the aqueous compositions useful for the production of decal transfer advantageously contain a wetting and levelling agent, which increases the adhesion of the ink and of the covercoat with the coated paper.
  • the machinery normally used for producing decal transfer are suitable without the need of any modification.
  • a decal transfer is produced using the traditional solvent based compositions.
  • a liquid medium with the following composition is prepared for the ink (parts are by weight) (Medium 1 ):
  • An ink is prepared by mixing and refining on three rollers mill: 40 parts by weight of Medium 1
  • a solvent-based composition is prepared (Covercoat Composition 1 ), having the following recipe:
  • the decal transfer (Decal transfer 1 ) is made following the traditional procedure, using as support a sheet of paper of 180g/m 2 , coated with a polysaccaride layer having a weight of 3,5 g/m 2 .
  • the image is printed by screen-printing, with two consecutive impressions (the first one with Ink 1- grey-blue, the second one with Ink 1 -purple); each impression is followed by desiccation for two hours at 25°C (Relative Humidity of air: 55%;
  • the Covercoat Composition 1 is then applyed by slik-screening covering all the surface of the decal transfer and so that the film weight is equal to 70 g/m 2 after being drying for 15 hours at 25°C (Relative Humidity of air: 55%;
  • the decal transfer (Decal transfer 1) may be detached by a quick immersion in water, it is on the average 40 micron thick and exhibit a breaking load at elongation of 25 Kg/cm 2 , measured by universal testing machine and applying load at the rate of 0,1 kg per second. It can be folded at least twice without breaking.
  • the Decal transfer 1 is then applyed onto an extruded, glazed and fired ceramic listel; after third firing at 900° C (maximum temperature), the image is perfectly transferred.
  • a decal transfer is produced by means of the aqueous compositions of the invention.
  • a water based liquid medium with the following composition is prepared for the ink (parts are by weight) (Medium 2):
  • An ink is prepared by mixing and refining on three rollers mill:
  • the decal transfer (Decal transfer 2) is made following the traditional procedure, using as support a sheet of paper coated with polyester of 295 g/m 2 .
  • the image is printed by screen-printing, with two consecutive impressions (the first one with Ink 2- gre-/blue, the second one with Ink 2-purple); each impression is followed by drying for two hours at 25°C (Relative Humidity of air:
  • the Covercoat Composition 2 is then applyed by slik-screening covering all the surface of the decal transfer and so that the film weight is equal to 120 g/m 2 after being desiccated for 12 hours at 25°C (Relative Humidity of air: 55%).
  • the decal transfer (Decal transfer 2) may be detached by simple traction, it is on the average 100 micron thick and exhibit a breaking load at elongation of 30
  • the Decal transfer 2 is then applyed on to an extruded, glazed and fired ceramic listel; after third firing at 900° C (maximum temperature), the image is perfectly transferred.
  • Example 3 A thick decal transfer is produced by means of the aqueous compositions of the invention.
  • a water based liquid medium with the following composition is prepared (parts are by weight) (Medium 3): Copolymer of methacrylic acid and butyl acrylate (5) 74,43
  • Sipacril 27390F manufactured by VEPI (Urgnano - BG, Italy), a 30% polymeric dispersion in water.
  • Vinavil EVA 2615/ manufactured by Vinavil (Villadossola - DO, Italy).
  • Anti-foam and wetting agent manufactured by Lamberti SpA manufactured by Lamberti SpA.
  • Dispersion 3 An solid dispersion (Dispersion 3) is prepared by mixing;
  • a water based composition is prepared (Covercoat Composition 3), having the following recipe (parts by weight):
  • the decal transfer (Decal transfer 3) is made following the traditional procedure, using as support a sheet of paper coated with polyester of 295 g/m 2 .
  • Dispersion 3 is applied by screen-printing so that the film weight is equal to 300g/m 2 after being dried for 18 hours at 25°C (Relative Humidity of air: 55%)
  • the Covercoat Composition 3 is applyed by screen-printing too, covering all the surface of the decal transfer and so that the film weight is equal to 100 g/m 2 after being dried for 1 hours at 40°C in forced air drying unit.
  • the decal transfer (Decal transfer 3) may be detached by simple traction, it is on the average 300 micron thick, its weight is about 400 g/m 2 and exhibit a breaking load at elongation of 30 Kg/cm 2 , measured by universal testing machine and applying load at the rate of 0.1 kg per second. It can be folded at least once without breaking.
  • the Decal transfer 3 is then applyed onto an extruded, glazed and fired ceramic listel; after third firing at 1180° C (maximum temperature) and firing cycle of 10 hours, the listel is coated by a continuous and uniform layer of ceramic glaze, perfectly vitrified.

Landscapes

  • Decoration By Transfer Pictures (AREA)
  • Glass Compositions (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

Composition aqueuse utile dans la fabrication d'une décalcomanie servant à décorer des articles céramiques ou en verre, qui permet d'éliminer l'émission de composés organiques volatils pendant la fabrication de la décalcomanie.
EP01272000A 2000-12-22 2001-12-11 Decalcomanie pour decorer des articles ceramiques ou en verre Withdrawn EP1358076A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
ITVA20000044 2000-12-22
IT2000VA000044A ITVA20000044A1 (it) 2000-12-22 2000-12-22 Decalcomanie per uso ceramico o vetrario
PCT/EP2001/014529 WO2002051649A2 (fr) 2000-12-22 2001-12-11 Decalcomanie pour decorer des articles ceramiques ou en verre

Publications (1)

Publication Number Publication Date
EP1358076A2 true EP1358076A2 (fr) 2003-11-05

Family

ID=11460832

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01272000A Withdrawn EP1358076A2 (fr) 2000-12-22 2001-12-11 Decalcomanie pour decorer des articles ceramiques ou en verre

Country Status (4)

Country Link
EP (1) EP1358076A2 (fr)
AU (1) AU2002217100A1 (fr)
IT (1) ITVA20000044A1 (fr)
WO (1) WO2002051649A2 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2799477B2 (es) * 2019-06-12 2021-05-17 Torrecid Sa Procedimiento de decoracion de vajilla mediante calca

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL280068A (fr) * 1965-03-31 1900-01-01
US4522864A (en) * 1979-09-06 1985-06-11 Dan C. Humason Decals and process for making same
EP0249486B1 (fr) * 1986-06-13 1992-01-22 Oscar Richard Fredrik af Ström Lech Décalcomanies, feuilles de support pour décalcomanies, et procédé pour transférer des images sur des substrats
MX172933B (es) * 1989-01-26 1994-01-24 Oscar Richard Frederik Af Stro Calcomanias y procesos para la transferencia de imagenes hacia substratos
US5073423A (en) * 1990-01-04 1991-12-17 Corning Incorporated Decalcomania
WO1995006564A1 (fr) * 1993-09-03 1995-03-09 Rexham Graphics Incorporated Procede de production d'image a jet d'encre et element d'enregistrement
US5741387A (en) * 1995-08-15 1998-04-21 Riverside Industries, Inc. Lithographic printing process and transfer sheet
JP3861305B2 (ja) * 1996-01-08 2006-12-20 住友化学株式会社 水性エマルジョン接着剤
EP0794212A1 (fr) * 1996-03-08 1997-09-10 Unitika Ltd. Dispersion aqueuse de résine de polyester et procédé pour sa préparation
JP3448306B2 (ja) * 1997-01-17 2003-09-22 ダイソー株式会社 アリル系架橋共重合体微粒子含有水系エマルション
NZ330371A (en) * 1997-06-09 1999-10-28 Kuraray Co Aqueous emulsion system having as dispersant a polyvinyl alcohol polymer and the condensate of an alkali metal salt of an aromatic sulfonic acid
US6096408A (en) * 1998-06-08 2000-08-01 Avery Dennison Corporation Heat-transfer label and method of decorating polyethylene-coated glass using same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO02051649A3 *

Also Published As

Publication number Publication date
AU2002217100A1 (en) 2002-07-08
ITVA20000044A1 (it) 2002-06-22
WO2002051649A2 (fr) 2002-07-04
ITVA20000044A0 (it) 2000-12-22
WO2002051649A3 (fr) 2003-07-24

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