WO2023104849A1 - Environmentally friendly medium for ceramic colours for indirect decoration of glass, porcelain, bone china, enamel, and ceramics - Google Patents

Environmentally friendly medium for ceramic colours for indirect decoration of glass, porcelain, bone china, enamel, and ceramics Download PDF

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Publication number
WO2023104849A1
WO2023104849A1 PCT/EP2022/084711 EP2022084711W WO2023104849A1 WO 2023104849 A1 WO2023104849 A1 WO 2023104849A1 EP 2022084711 W EP2022084711 W EP 2022084711W WO 2023104849 A1 WO2023104849 A1 WO 2023104849A1
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WIPO (PCT)
Prior art keywords
printing medium
use according
anyone
binder
total weight
Prior art date
Application number
PCT/EP2022/084711
Other languages
French (fr)
Inventor
Andreas Schulz
Silke Schäfer
Julian Schütze
Original Assignee
Ferro Gmbh
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Publication date
Application filed by Ferro Gmbh filed Critical Ferro Gmbh
Priority to EP22834515.3A priority Critical patent/EP4444805A1/en
Publication of WO2023104849A1 publication Critical patent/WO2023104849A1/en

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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
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • 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
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • 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

  • the present invention relates to the use of a composition for the preparation of decorations on a surface of a substrate, comprising at least one specific printing medium for the preparation of decorations on the surface of a refractory substrate, comprising glass, porcelain, bone china, enamel, and ceramics.
  • the ceramic ink is suitable for indirect printing, in particular for the process of decalcomania.
  • Decalcomania is a decorative technique by which engravings and prints may be transferred to the surface of substrates of, for example, glass, bone china, enamel, porcelain, and ceramics.
  • Today, the shortened version of decalcomania is "decal”.
  • the desired decoration is usually applied to the surface of a suitable substrate by means of conventional decoration techniques, in particular indirect printing processes, and baked in a known manner at temperatures in the range from usually 500 to 1400 °C.
  • a paste comprising a printing medium together with an organic binder and inorganic colouring components are usually used.
  • the paste media for matching inorganic colouring components often contain hazardous substances.
  • the used media formulations comprise CMR-assed or even SVHC-assed components, whereby the term CMR (cancerogenic mutagen reprotoxic) hereby refers to carcinogenic, mutagenic and fertility-endangering substances, and the term SVHC refers to a substance of very high concern (SVHC) that has been identified under the European REACH Regulation as having particularly hazardous properties and that may have serious effects on human health or the environment.
  • EP 0 599 105 A discloses a colour paste suitable for stoving at 500 to 1400 °C on surfaces of glass, porcelain, or ceramic.
  • the paste consists essentially of at least one colour producing inorganic components selected from the group consisting of storing stable pigments and colour frits, a printing medium comprising a polymeric organic binder system dissolved as a clear solution or a gel in an organic solvent system, wherein the solvent system contains at least 70 to 100% by weight of at least one isoparaffin having a boiling point in the range of from above 150 to 250 °C, at least one solvating plasticiser and at least one solvent selected from the group consisting of alcohols, ethers and esters.
  • the solvents used in the examples of EP 0 599 105 A are systemic health hazard.
  • WO 2007/014131 A discloses a ceramic correction fluid comprising a thermoplastic binder; particles selected from the group consisting of translucent particles, opaque particles, transparent particles, and combinations thereof; and a liquid medium; wherein said thermoplastic binder is present at a concentration of from about 15 percent to about 90 percent by weight of said thermoplastic binder and said particles; said particles are present at a concentration of at least about 10 percent by weight of said thermoplastic binder and said particles; and when said ceramic correction fluid is applied to a glass substrate and allowed to stand for about twenty four hours at a temperature of about 22 °C, said ceramic correction fluid has a tape susceptibility of less than about 15 percent.
  • the materials used in the example section of said document may also cause significant health difficulties.
  • the hazard classification of the previous media is mainly based on the solvents used. Replacing these hazard solvents by less hazard solvents greatly worsens the wetting of the inorganic inks, so that only a low matching ratio and thus poorer opacity are achieved. Moreover, the increase in viscosity with respect to the ceramic paste results in inadequate printing behaviour.
  • an organic printing medium for the use in compositions for the preparation of decorations on a surface of a substrate, wherein the wetting of inorganic inks is sufficient realized and health hazards for users due to the used solvent are reduced or even avoided.
  • an organic printing medium for the use in compositions for the preparation of decorations on a surface of a substrate, wherein a high matching ratio is achieved and health hazards for users due to the used solvent are reduced or even avoided.
  • an organic printing medium for the use in compositions for the preparation of decorations on a surface of a substrate, wherein an improved opacity of the resulting decal is achieved and health hazards for users due to the used solvent are reduced or even avoided.
  • the organic printing medium provided by the present invention allows a good wetting of inorganic colours to be used in combination with the printing medium, whereby a high matching ratio and an improved opacity is achieved.
  • the organic printing provided by the present invention medium comprises organic solvents which do not create health hazards for users.
  • the organic printing medium provided by the present invention essentially consists of organic solvents which do not create health hazards for uses.
  • the present invention relates to the use of a composition for the preparation of decorations on a surface of a substrate, comprising a. at least one printing medium, comprising a polymeric organic binder system in at least one organic solvent, for indirect printing.
  • composition is thereby characterized in that the at least one organic solvent comprised in the printing medium has an evaporation number VD between 80 and 600 according to DIN 53 170.
  • the evaporation number VD is the ratio of the evaporation time of the liquid substance or liquid mixture with respect to the evaporation time of the reference liquid diethyl ether at room temperature and normal pressure.
  • the evaporation time is the time it takes for the liquid to evaporate below its boiling point by using the following relationship
  • a suitable test method is described in DIN test method DIN 53170.
  • the solvents to be used in the printing medium have a specific Hansen Solubility Parameter.
  • the Hansen solubility parameter consist of a disperse fraction from London interactions (dd), a fraction from dipolar interactions (d p ) and a fraction for the hydrogen bonds (dh).
  • the Hansen Solubility Parameters (HSP) were developed by Charles M. Hansen as a way of predicting if one material will dissolve in another and form a solution. They are based on the idea that "like dissolves like" where one molecule is defined as being 'like' another if it bonds to itself in a similar way.
  • each solvent in the sense of the present invention is given three Hansen parameters, each generally measured in .
  • Suitable solvents according to the present invention have a disperse fraction from London interactions (dd) of preferably between 13 and 17 .
  • Suitable solvents according to the present invention have a fraction from dipolar interactions (d p ) of preferably between 1.5 and 8.5 .
  • Suitable solvents according to the present invention have a disperse fraction for the hy- drogen bonds (dh) of preferably between 3 and 15 .
  • Suitable solvents according to the present invention have, more preferably, a disperse fraction from London interactions ) of between
  • Suitable solvents according to the present invention have, more preferably, a disperse fraction from London interactions (dd) of between disperse fraction for the hydrogen bonds (dh) of between 3 and
  • Suitable solvents according to the present invention have, more preferably, a fraction from dipolar interactions (d p ) of between 1.5 and 8.5 and a disperse fraction for the hydrogen bonds (dh) of between 3 and 15
  • Suitable solvents according to the present invention have, most preferably, a disperse fraction from London interactions (dd) of between 13 and 17 a fraction from dipolar interactions (d p r) of between 1.5 and 8.5 and a disperse fraction for the hydrogen bonds (dh) of between
  • a picture layer consisting of or containing the printing medium, inorganic pigment and flux is applied to a carrier with a water-soluble size coating or a wax layer, and this picture layer is filmed over immediately or after application of an intermediate layer containing a glass flux.
  • the decorated sample is fired between 500 und 1400 °C.
  • DE 12 32 168 a, EP 0 863 187 a, DE 43 37 648 A, DE 43 10 250 A, EP 0 195 239 A and EP 1 358 279 A by way of example.
  • the solvents of the printing medium preferably have the above-mentioned characteristics for the evaporation number and the Hansen solubility parameter
  • the technical object of the present invention can be solved.
  • the printing mediums falling within this definition provide a good wetting of inorganic inks, a high matching ratio and an improved opacity.
  • the organic solvents comprised in the printing medium possess the above-described evaporation number.
  • the organic solvent is a poor solvent for the binder, it will leave the medium more quickly than a good organic solvent with the same evaporation number.
  • evaporation numbers according to the definition of DIN 53170 are easily accessible for the person skilled in the art, for example from Ullmann’s Encyclopedia of Technical Chemistry, 4 th , revised and expanded edition, volume 16, page 305 table 7, and in case no information about the evaporation number are disclosed in the prior art, the evaporation numbers can be easily derived from the methods described above and/or described in the DIN 53170.
  • printing mediums used in the present invention comprising organic solvent with the above-mentioned evaporation number VD and/or Hansen Solubility Parameters do not create health hazards for users of the claimed compositions. This applies especially to the solvents used.
  • the evaporation numbers of the printing medium to be used in the claimed composition are 80 to 600, more preferably 85 to 550, especially preferred 90 to 450.
  • Hansen Solubility Parameters are also easily accessible for the person skilled in the art and in case no information about the evaporation number are disclosed in the prior art; the Hansen Solubility Parameters are disclosed, for example, in Ullmann’s Encyclopedia of Technical Chemistry, 4 th , revised and expanded edition, volume 16, page 283.
  • the complete printing medium is composed of solvents fulfilling the afore-mentioned range of evaporation numbers and Hansen Solubility Parameters, as long as at least 25 to 75 wt.-%, preferably at least 30 to 65 wt.-%, more preferably at least 40 to 60 wt.-%, each based on the total amount of the printing medium, of the printing medium is composed of compounds fulfilling the above-mentioned range of the evaporation number and the Hansen Solubility Parameter.
  • all solvents of the printing medium fulfil the above- mentioned definition of the evaporation number and the Hansen Solubility Parameters.
  • Respective organic solvents to be used in the claimed composition fulfilling the above- mentioned requirement of the evaporation number VD between 90 and 600 according to DIN 53170 and the Hansen Solubility Parameters are described in the following in more detail.
  • the solvent to be used in the printing medium comprises an ether and/or ester.
  • the ether and/or ester to be used in the present invention which possesses the above- mentioned evaporation number and Hansen Solubility Parameters are preferably a glyc- idyl ether and/or a glycidyl ester.
  • the glycol ether is preferably a compound in which the hydrogen atom of one or each hydroxyl group in a dimer to tetramer of a dihydric alcohol having 2 to 4 carbon atoms is substituted by a C1-6 alkyl group.
  • the glycol ether according to the invention is preferably an alkyl ether of diethylene glycol or an alkyl ether of dipropylene glycol.
  • it may preferably be a diethylene glycol ether, such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether or diethylene glycol dibutyl ether, or a dipropylene glycol ether, such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol mono-n-butyl ether or dipropylene glycol
  • glycol ether type solvent only one kind may be used, or two or more kinds may be used in combination.
  • the ester used as the solvent in the present invention can be any glycol ester.
  • glycol ester solvents include ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PMA; 2-methoxy-1 -methylethyl acetate; 1-methoxy-2-propyl acetate), dipropylene glycol monomethyl ether acetate, propylene glycol diacetate and the like.
  • PMA 2-methoxy-1 -methylethyl acetate
  • 1-methoxy-2-propyl acetate dipropylene glycol monomethyl ether acetate
  • glycol ester type solvent only one kind may be used, or two or more kinds may be used in combination.
  • the printing medium according to the present invention is characterized in that the organic solvent consist essentially of glycol ether and/or glycol ester.
  • the composition according to the present invention is characterised in that the printing medium comprises at least one glycol ether in an amount of from 5 to 50 wt.-%, preferably 10 to 40 wt.-%, more preferably from 15 to 30 wt.-%, based on the total weight of the printing medium.
  • the composition according to the present invention is characterised in that the printing medium comprises at least one glycol ester in an amount of from 10 to 60 wt.-%, preferably 15 to 50 wt.-%, more preferably from 20 to 40 wt.-%, based on the total weight of the printing medium.
  • the solvent used in the printing medium is preferably predominantly free of aromatics and alkanes.
  • predominantly free of aromatics and alkanes means that the printing medium comprises less than 1 wt.-%, preferably less than 0.75 wt.-%, more preferably less than 0.5 wt.-%, more preferably less than 0.25 wt.-%, more preferably less than 0.20 wt.-%, more preferably less than 0.1 wt.-%, aromatics, and alkanes.
  • the printing medium of the present invention comprises preferably a binder.
  • the printing medium comprise an acrylic resin as a binder.
  • the printing medium comprises a copolymer of methyl methacrylate and butyl methacrylate as a binder.
  • the molecular weight of the binder is not particularly restricted.
  • the binder to be used in the printing medium comprises usually a binder with a molecular weight of from 10000 to 250000 g/mol, preferably 20000 to 200000 g/mol, more preferably of from 25000 to 180000 g/mol.
  • the molecular weight is measured by gel permeation chromatography according to DIN 55672-1.
  • a further suitable binder system is a polyaminoamide.
  • Polyaminoamides are well known epoxide curing agents (publication of Bakelit-AG, page 5, column 3, DE 37 11 947 A1). “Polyaminoamide” is a generic term which describes compounds which contain several free (active) amino groups and at least one amide function per molecule (“International Organisation for Standardisation”). Essentially, they are reaction products of carboxylic acids or their esters with polyamines. Polyaminoamides are obtained primarily from the condensation reaction between a polymeric fatty acid such as a dimeric or trimeric acid, and a polyamine such as e.g. polyethylene polyamine. Examples of these polyaminoamides are described by the following formula
  • Suitable binders are polyamide resins.
  • Suitable polyamide resins are those which are used as lacquer resins and hot-melt adhesives.
  • the softening point of the polyamide resins is preferably in the range 50 to 150 °C, in particular in the range 80 to 120 °C.
  • They are generally aliphatic polyamides with structural elements from a dicarboxylic acid and/or a diamine with more than 8 carbon atoms; the dicarboxylic acid components in the polyamides are preferably dimeric fatty acids.
  • the printing medium comprises the afore-mentioned binder in an amount of from 10 to 70 wt.-%, preferably 20 to 60 wt.-%, more preferably from 28 to 55 wt.-%, based on the total weight of the printing medium.
  • the organic printing medium according to the present invention may further comprise at least one additive, selected from the group consisting of a plasticizer, a defoamer, a dispersing agent (or wetting agent), a thixotropic agent or rheology additive and any suitable mixtures thereof.
  • the plasticizer may be present in an amount of from 0.01 to 7 wt.-%, preferably of from 0.5 to 6 wt.-%, more preferably of from 1 to 5 wt.-%, based on the total weight of the printing medium
  • the defoamer may be comprised in an amount of from 0.01 to 5 wt.-%, preferably of from 0.02 to 2.5 wt.-%, more preferably of from 0.05 to 1 .5 wt.-%, based on the total weight of the printing medium.
  • the defoamer may be selected from a polysiloxane and/or a silicone oil as a defoamer.
  • Further suitable defoamer (deaerator) are polymer defoamer and mineral oil defoamer which are available for example form the company BYK-Chemie GmbH or from the company Evonik.
  • a dispersing agent is preferably used.
  • Dispersing agents in the sense of the present invention are specialized wetting agents that wet out surfaces of particles during the dispersion process, and subsequently stabilize the dispersion such that the particles do not re-agglomerate. Dispersing agents prevent re-agglomeration by either electrostatic stabilization or by steric hindrance. Dispersing agents consist of a polar head that “attaches” to the particle to be dispersed, and a polymer chain that is compatible in the media in which the particle is being dispersed.
  • the dispersing agent may be comprised, in a first embodiment, in an amount of from 1 to 5 wt.-%, preferably of from 1.25 to 4 wt.-%, more preferably of from 1.5 to 3 wt.-%, based on the total weight of the printing medium.
  • the dispersing agent may be comprised, in a second embodiment, in an amount of from 0.05 to 15 wt.-%, preferably of from 0.1 to 10 wt.-%, more preferably of from 0.5 to 5 wt.-%, based on the total weight of the printing medium.
  • the dispersing agent may function also as a wetting agent in the printing medium used in the present invention.
  • the dispersing agent wetting agent
  • the dispersing agent is an additive containing groups with affinity for particles.
  • groups can be selected from the group, consisting of acidic groups, such as carboxylic acids, phosphoric acids; basic groups, such as amines; and neutralized groups or neutral groups.
  • These functional groups can be attached to a low molecular weight resin or polymer with a molecular weight of preferably from 1000 to 5000 g/mol or higher molecular weight resin or polymer (above 5000 g/mol).
  • the resins can be aliphatic, polyester or a polyether. By using an aliphatic resin, a polyester resin or a polyether resin, it is possible to adjust the polarity of the dispersing agent.
  • soy lecithin-based additives and oil-modified polyesters are used as a dispersing agent (wetting agent) in the printing medium used in the present invention.
  • composition dispersing agent may be selected further from a polyether phosphate and/or a polyurethane.
  • dispersing agents are amine salts of polyether ester, amine salts of polyether phosphates, aliphatic polycarboxylic acids, amine salts of polyetherester carboxylic acids, anionic surfactants, amine salts of polyetherester/acrylic polymers, and amine salts of polyetherester/acrylic polymers.
  • dispersing agents are fatty acids, phosphonic acid acetates, polyurethanes, polyamines, acrylate polymers and CPT acrylates.
  • dispersing agents are (solutions of) polycarboxylic acid salts of polyamine amides, alkyl ammonium salts of polymeric acid esters, phosphoric acid esters, (solutions of) high molecular weight block copolymer with pigment affine groups, (solutions of) modified polyurethanes, (solutions of) polymeric phosphoric acid ester alkyl ammonium salts, acrylate copolymers with basic, piment-affine groups, block copolymers with pigment affine groups, (solutions of) structured acrylate copolymers with pigment- affine groups and (solutions of) polyacrylates.
  • Suitable thixotropic agents and rheology additives are, for example, solutions of a modified urea (such as Rheobyk-410), solution of a high molecular weight urea-modified nonpolar polyamide (such as Rheobyk-431), solutions of a modified polyamide (such as Rheobyk-440), micronized, modified, rheological active amide (such as Rheobyk-7503), hydrogenated castor oil, hydrogenated amid-modified hydrogenated castor oil, amides, oxidized polyethylene, poly urea, castor oil, diamond waxes and polyamide waxes, and pyrogenic silica.
  • a modified urea such as Rheobyk-410
  • solution of a high molecular weight urea-modified nonpolar polyamide such as Rheobyk-431
  • solutions of a modified polyamide such as Rheobyk-440
  • micronized, modified, rheological active amide such as Rheoby
  • the above-described printing medium is preferably composed of components which are non-classified in the Globally Harmonized System of Classification and Labelling of Chemicals (GHS). Therefore, organic solvents as described above are combined with dispersants described above to balance the characteristics of the printing medium as initially discussed and to fulfil, at the same time, the requirement of providing a printing medium being non-classified in the Globally Harmonized System of Classification and Labelling of Chemicals (GHS).
  • GLS Globally Harmonized System of Classification and Labelling of Chemicals
  • GCS Globally Harmonized System of Classification and Labelling of Chemicals
  • Core elements of the GHS include standardized hazard testing criteria, universal warning pictograms, and harmonized safety data sheets which provide users of dangerous goods with a host of information.
  • the system acts as a complement to the UN Numbered system of regulated hazardous material transport. Implementation is managed through the UN Secretariat.
  • Printing mediums used according to the present invention preferably only comprise compounds which fulfil at least one of the following requirements according to the GHS standard: no carcinogen labelling, no mutagenic labelling, no reprotoxic labelling, no sensitization, no skin irritation, not easily flammable, and not causing drowsiness.
  • the organic printing medium is not classified under GHS system for carcinogen labelling, mutagenic labelling and reprotoxic labelling.
  • the organic printing medium is not classified under GHS system for carcinogen labelling, mutagenic labelling, reprotoxic labelling, sensitization labelling, skin irritation labelling and drowsiness labelling.
  • the organic printing medium is not classified under GHS system for carcinogen labelling, mutagenic labelling, reprotoxic labelling, sensitization labelling, skin irritation labelling, drowsiness labelling and flammable labelling.
  • Printing used mediums according to the present invention preferably only comprise compounds which fulfil at least two, more preferably at least three, more preferably at least four, more preferably at least five, more preferably at least six, more preferably at least seven of the above-mentioned requirements according to the GHS standard.
  • all compounds to be used in the printing medium do not have any labelling of the GHS system.
  • the use of the printing medium for indirect printing the use of components of the printing medium that do not have any labelling is preferred because the printing medium is also used in print shops and printing companies that do not have complete safety devices, such as air outlet apparatuses.
  • the colour producing inorganic components in the colour pastes may be so called colour frits, i.e. fritted glasses containing colour producing metal oxides and/or inorganic pigments known in the art, provided they are sufficiently stable to stoving.
  • colour frits include in particular lead borosilicate glasses containing CuO, CoO, MnO, Fe2Oa.
  • pigments include oxides of the elements Cr, Mn, Fe, Co, Ni, Cu and Cd and their mixed oxides with AI2O3, TiC>2, ZnO, SnC>2, e. g. spinels and titanates; also, sulphides and selenides of Cd, in particular in the form of glazing stable inclusion pigments.
  • glass flux is used mainly to denote glass frits which melt at the stoving temperature.
  • Preferred glass frits have a low melting point, e. g. in the region of 450 °C to 800 °C. The melting point and hence the choice of glass depends on the article to be decorated.
  • Borosilicate glasses containing one or more oxides of Li, Na, K, Mg, Ca, Al, Ti, Zr, Sn, Pb, Cd, Sb, Bi are customarily used.
  • a glass flux may also be a combination of SiC>2 or silicates and B2O3 with one or more of the above-mentioned oxides and fluxes such as fluorides, provided that glass formation is possible under the stoving conditions.
  • the present invention relates to the use of a composition
  • a composition comprising a. at least one printing medium, comprising a polymeric organic binder system in at least one organic solvent, whereby the printing medium comprises one or more dispersing agents (dispersants, wetting additives), one or more defoamers, one or more binders, optionally one or more plasticizers, one or more solvents and optionally one or more thixotropic agents, whereby the solvent being selected so as to be predominantly free of aromatics and alkanes, the Hansen solubility parameters for the solvent being have a disperse fraction from London interactions (dd) of between 13 and fraction from dipolar inter- actions (d p ) of preferably between 1.5 and 8.5 disperse for the hydrogen bonds (dh) of between 3 and 15 and the evaporation number being between 90 and 600 according to DIN 153 170.
  • dispersing agents dispersants, wetting additives
  • defoamers one or more binders
  • plasticizers optionally one or
  • the printing medium comprises less than 1 wt.-%, preferably less than 0.75 wt.-%, more preferably less than 0.5 wt.-%, more preferably less than 0.25 wt.-%, more preferably less than 0.20 wt.-%, more preferably less than 0.1 wt.-%, aromatics, and alkanes.
  • composition described above is used for the decoration of any suitable substrate, such as substrates selected from glass, porcelain, bone china, enamel and ceramics, by the process of indirect printing.
  • composition comprising a. at least one printing medium, comprising a polymeric organic binder system in at least one organic solvent for the preparation of decorations on a surface of a substrate by indirect printing, wherein the at least one printing medium has an evaporation number between 80 and 600 according to DIN 153 170.
  • organic solvent comprises an ether and/or ester.
  • organic solvent comprises glycol ether and/or glycol ester.
  • the printing medium comprises at least one glycol ether in an amount of from 5 to 50 wt.-%, preferably 10 to 40 wt.-%, more preferably from 15 to 30 wt.-%, based on the total weight of the printing medium.
  • the printing medium comprises at least one glycol ester in an amount of from 10 to 60 wt.-%, preferably 15 to 50 wt.-%, more preferably from 20 to 40 wt.-%, based on the total weight of the printing medium.
  • the printing medium comprise an acrylic resin as a binder.
  • the printing medium comprises a copolymer of methyl methacrylate and butyl methacrylate as a binder.
  • the printing medium comprises a binder with a molecular weight of from 10000 to 250000 g/mol, preferably 20000 to 200000 g/mol, more preferably of from 25000 to 180000 g/mol.
  • the printing medium comprises a binder in an amount of from 10 to 70 wt.-%, preferably 20 to 60 wt.-%, more preferably from 28 to 55 wt.-%, based on the total weight of the printing medium.
  • composition further comprises at least one additive, selected from the group consisting of a plasticizer, a defoamer, a dispersing agent, a thixotropic agent or rheology additive and any suitable mixtures thereof.
  • the printing medium comprises a defoamer in an amount of from 0.01 to 5 wt.-%, preferably of from 0.02 to 2.5 wt.-%, more preferably of from 0.05 to 1.5 wt.-%, based on the total weight of the printing medium.
  • composition further comprises a polysiloxane and/or a silicone oil as a defoamer.
  • the printing medium comprises a dispersing agent in an amount of from 0.5 to 5 wt.-%, preferably of from 1.25 to 4 wt.-%, more preferably of from 1.5 to 3 wt.-%, based on the total weight of the printing medium.
  • composition further comprises a polyether phosphate and a polyurethane as a dispersing agent.
  • composition further comprises a plasticizer in an amount of from 0.01 to 7 wt.-%, preferably of from 0.5 to 6 wt.-%, more preferably of from 1 to 5 wt.-%, based on the total weight of the printing medium.
  • composition additionally comprises at least one colouring inorganic component of a stoving-stable pigment and/or a colour frit.
  • the substrate is selected from glass, porcelain, bone china, enamel and ceramics.
  • the following organic printing media are prepared by mixing the indicated components at room temperature in the indicated amounts, whereby the solvent is added with the binder under stirring. Thereafter, the plasticizer, the additives and the thixotropic agent are added while stirring. The resulting composition is heated to a temperature of 45 to 75 °C and maintained at this temperature for a period of 30 min to 2 hours. Thereafter, the resulting composition is cooled to room temperature.
  • One specific formulation is shown below:

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

Described is the use of a composition for the preparation of decorations on a surface of a substrate by indirect printing, comprising at least one colouring inorganic component of a stoving-stable pigment and/or a colour frit; wherein the at least one printing medium has an evaporation number between 80 and 600 according to DIN 153 170.

Description

Environmentally friendly medium for ceramic colours for indirect decoration of glass, porcelain, bone china, enamel, and ceramics
Specification
The present invention relates to the use of a composition for the preparation of decorations on a surface of a substrate, comprising at least one specific printing medium for the preparation of decorations on the surface of a refractory substrate, comprising glass, porcelain, bone china, enamel, and ceramics. The ceramic ink is suitable for indirect printing, in particular for the process of decalcomania.
Decalcomania is a decorative technique by which engravings and prints may be transferred to the surface of substrates of, for example, glass, bone china, enamel, porcelain, and ceramics. Today, the shortened version of decalcomania is "decal".
Thereby, the desired decoration is usually applied to the surface of a suitable substrate by means of conventional decoration techniques, in particular indirect printing processes, and baked in a known manner at temperatures in the range from usually 500 to 1400 °C. For this purpose, a paste comprising a printing medium together with an organic binder and inorganic colouring components are usually used.
One main disadvantage of the paste used for the above-described decal technology is that the paste media for matching inorganic colouring components often contain hazardous substances. Frequently, the used media formulations comprise CMR-assed or even SVHC-assed components, whereby the term CMR (cancerogenic mutagen reprotoxic) hereby refers to carcinogenic, mutagenic and fertility-endangering substances, and the term SVHC refers to a substance of very high concern (SVHC) that has been identified under the European REACH Regulation as having particularly hazardous properties and that may have serious effects on human health or the environment.
So far, there are no environmentally friendly media for the application of decals for the decoration of glass, porcelain, bone china, enamel, and ceramics. All previous media for this application were classified as hazardous substances and had to be used with restrictions relevant to occupational safety.
EP 0 599 105 A discloses a colour paste suitable for stoving at 500 to 1400 °C on surfaces of glass, porcelain, or ceramic. The paste consists essentially of at least one colour producing inorganic components selected from the group consisting of storing stable pigments and colour frits, a printing medium comprising a polymeric organic binder system dissolved as a clear solution or a gel in an organic solvent system, wherein the solvent system contains at least 70 to 100% by weight of at least one isoparaffin having a boiling point in the range of from above 150 to 250 °C, at least one solvating plasticiser and at least one solvent selected from the group consisting of alcohols, ethers and esters. The solvents used in the examples of EP 0 599 105 A are systemic health hazard.
WO 2007/014131 A discloses a ceramic correction fluid comprising a thermoplastic binder; particles selected from the group consisting of translucent particles, opaque particles, transparent particles, and combinations thereof; and a liquid medium; wherein said thermoplastic binder is present at a concentration of from about 15 percent to about 90 percent by weight of said thermoplastic binder and said particles; said particles are present at a concentration of at least about 10 percent by weight of said thermoplastic binder and said particles; and when said ceramic correction fluid is applied to a glass substrate and allowed to stand for about twenty four hours at a temperature of about 22 °C, said ceramic correction fluid has a tape susceptibility of less than about 15 percent. The materials used in the example section of said document may also cause significant health difficulties.
The hazard classification of the previous media is mainly based on the solvents used. Replacing these hazard solvents by less hazard solvents greatly worsens the wetting of the inorganic inks, so that only a low matching ratio and thus poorer opacity are achieved. Moreover, the increase in viscosity with respect to the ceramic paste results in inadequate printing behaviour.
Therefore, it is the object of the present invention to provide an organic printing medium for the use in compositions for the preparation of decorations on a surface of a substrate, wherein health hazards for users due to the used solvent are reduced or even avoided.
Furthermore, it is the object of the present invention to provide an organic printing medium for the use in compositions for the preparation of decorations on a surface of a substrate, wherein the wetting of inorganic inks is sufficient realized and health hazards for users due to the used solvent are reduced or even avoided.
Furthermore, it is the object of the present invention to provide an organic printing medium for the use in compositions for the preparation of decorations on a surface of a substrate, wherein a high matching ratio is achieved and health hazards for users due to the used solvent are reduced or even avoided.
Moreover, it is the object of the present invention to provide an organic printing medium for the use in compositions for the preparation of decorations on a surface of a substrate, wherein an improved opacity of the resulting decal is achieved and health hazards for users due to the used solvent are reduced or even avoided.
These objects are solved in the present invention by the use of a specific selection of solvents and, in preferred embodiments, by using, in addition to these specific solvents, special dispersants.
The adjustment of the solvent and the dispersant to each other according to the present invention allows to solve one or more of the objects addressed above.
In particular, the organic printing medium provided by the present invention allows a good wetting of inorganic colours to be used in combination with the printing medium, whereby a high matching ratio and an improved opacity is achieved. Moreover, the organic printing provided by the present invention medium comprises organic solvents which do not create health hazards for users. In preferred embodiments, the organic printing medium provided by the present invention essentially consists of organic solvents which do not create health hazards for uses.
That said, the present invention relates to the use of a composition for the preparation of decorations on a surface of a substrate, comprising a. at least one printing medium, comprising a polymeric organic binder system in at least one organic solvent, for indirect printing.
The composition is thereby characterized in that the at least one organic solvent comprised in the printing medium has an evaporation number VD between 80 and 600 according to DIN 53 170.
The evaporation number VD is the ratio of the evaporation time of the liquid substance or liquid mixture with respect to the evaporation time of the reference liquid diethyl ether at room temperature and normal pressure. The evaporation time is the time it takes for the liquid to evaporate below its boiling point by using the following relationship
VD = VDZ (substance, mixture) / VDZ (ether) with VDZ = evaporation time.
The evaporation time of ether is thereby set as VDZ = 1. The respective measurement method for the evaporation time is determined at a temperature T = 23 ± 2 °C and a relative humidity of 50 ± 6 %, whereby equal volumes are evaporated. A suitable test method is described in DIN test method DIN 53170.
In a further embodiment of the present invention, the solvents to be used in the printing medium have a specific Hansen Solubility Parameter. The Hansen solubility parameter consist of a disperse fraction from London interactions (dd), a fraction from dipolar interactions (dp) and a fraction for the hydrogen bonds (dh). The Hansen Solubility Parameters (HSP) were developed by Charles M. Hansen as a way of predicting if one material will dissolve in another and form a solution. They are based on the idea that "like dissolves like" where one molecule is defined as being 'like' another if it bonds to itself in a similar way.
Specifically, each solvent in the sense of the present invention is given three Hansen parameters, each generally measured in .
Figure imgf000004_0001
Suitable solvents according to the present invention have a disperse fraction from London interactions (dd) of preferably between 13 and 17 .
Figure imgf000004_0002
Suitable solvents according to the present invention have a fraction from dipolar interactions (dp) of preferably between 1.5 and 8.5 .
Figure imgf000005_0001
Suitable solvents according to the present invention have a disperse fraction for the hy- drogen bonds (dh) of preferably between 3 and 15 .Suitable solvents according to
Figure imgf000005_0002
the present invention have, more preferably, a disperse fraction from London interactions ) of between
Figure imgf000005_0009
Suitable solvents according to the present invention have, more preferably, a disperse fraction from London interactions (dd) of between disperse fraction for the hydrogen bonds (dh) of between 3 and
Figure imgf000005_0003
Suitable solvents according to the present invention have, more preferably, a fraction from dipolar interactions (dp) of between 1.5 and 8.5 and a disperse fraction for
Figure imgf000005_0004
the hydrogen bonds (dh) of between 3 and 15
Figure imgf000005_0005
Suitable solvents according to the present invention have, most preferably, a disperse fraction from London interactions (dd) of between 13 and 17 a fraction from dipolar
Figure imgf000005_0006
interactions (dp r) of between 1.5 and 8.5 and a disperse fraction for the hydrogen
Figure imgf000005_0007
bonds (dh) of between
Figure imgf000005_0008
With the decalcomanias required for indirect printing, a picture layer consisting of or containing the printing medium, inorganic pigment and flux is applied to a carrier with a water-soluble size coating or a wax layer, and this picture layer is filmed over immediately or after application of an intermediate layer containing a glass flux. Depending on the substrate, the decorated sample is fired between 500 und 1400 °C. Reference is made to DE 12 32 168 a, EP 0 863 187 a, DE 43 37 648 A, DE 43 10 250 A, EP 0 195 239 A and EP 1 358 279 A by way of example.
In the following, at first the printing medium is described in detail, whereby the solvents of the printing medium preferably have the above-mentioned characteristics for the evaporation number and the Hansen solubility parameter
Printing medium
According to the present invention, it has been found out that by specifically selecting the printing medium comprising an organic solvent having an evaporation number VD and a Hansen Solubility Parameter in the above-mentioned ranges, the technical object of the present invention can be solved. The printing mediums falling within this definition provide a good wetting of inorganic inks, a high matching ratio and an improved opacity.
As a major part of the printing medium is composed of organic solvents, it might be sufficient under the scope of the present invention that the organic solvents comprised in the printing medium possess the above-described evaporation number. However, it is necessary to consider the influence of the binder system to be used in the printing medium. If the organic solvent is a poor solvent for the binder, it will leave the medium more quickly than a good organic solvent with the same evaporation number.
The evaporation numbers according to the definition of DIN 53170 are easily accessible for the person skilled in the art, for example from Ullmann’s Encyclopedia of Technical Chemistry, 4th, revised and expanded edition, volume 16, page 305 table 7, and in case no information about the evaporation number are disclosed in the prior art, the evaporation numbers can be easily derived from the methods described above and/or described in the DIN 53170. In addition, printing mediums used in the present invention comprising organic solvent with the above-mentioned evaporation number VD and/or Hansen Solubility Parameters do not create health hazards for users of the claimed compositions. This applies especially to the solvents used.
In preferred embodiments of the present invention, the evaporation numbers of the printing medium to be used in the claimed composition are 80 to 600, more preferably 85 to 550, especially preferred 90 to 450.
Moreover, it was found out that also the above-mentioned Hansen Solubility Parameters of the organic solvents used in the printing medium according to the present invention plays a role in the achievement of the above-referenced objection meaning that organic solvents falling within this definition provide a good wetting of inorganic inks, a high matching ratio and an improved opacity of the printing medium.
The Hansen Solubility Parameters are also easily accessible for the person skilled in the art and in case no information about the evaporation number are disclosed in the prior art; the Hansen Solubility Parameters are disclosed, for example, in Ullmann’s Encyclopedia of Technical Chemistry, 4th, revised and expanded edition, volume 16, page 283.
It is not necessary in the sense of the present invention, that the complete printing medium is composed of solvents fulfilling the afore-mentioned range of evaporation numbers and Hansen Solubility Parameters, as long as at least 25 to 75 wt.-%, preferably at least 30 to 65 wt.-%, more preferably at least 40 to 60 wt.-%, each based on the total amount of the printing medium, of the printing medium is composed of compounds fulfilling the above-mentioned range of the evaporation number and the Hansen Solubility Parameter.
In a preferred embodiment, however, all solvents of the printing medium fulfil the above- mentioned definition of the evaporation number and the Hansen Solubility Parameters. Respective organic solvents to be used in the claimed composition fulfilling the above- mentioned requirement of the evaporation number VD between 90 and 600 according to DIN 53170 and the Hansen Solubility Parameters are described in the following in more detail.
In a first aspect of the present invention, the solvent to be used in the printing medium comprises an ether and/or ester.
The ether and/or ester to be used in the present invention which possesses the above- mentioned evaporation number and Hansen Solubility Parameters are preferably a glyc- idyl ether and/or a glycidyl ester.
In the present invention, the glycol ether is preferably a compound in which the hydrogen atom of one or each hydroxyl group in a dimer to tetramer of a dihydric alcohol having 2 to 4 carbon atoms is substituted by a C1-6 alkyl group.
The glycol ether according to the invention is preferably an alkyl ether of diethylene glycol or an alkyl ether of dipropylene glycol. Specifically, it may preferably be a diethylene glycol ether, such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether or diethylene glycol dibutyl ether, or a dipropylene glycol ether, such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol mono-n-butyl ether or dipropylene glycol monoisobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether or dipropylene glycol dibutyl ether. The glycol ethers of the invention can be used alone or in combination as a mixture of two or more of them.
As the glycol ether type solvent, only one kind may be used, or two or more kinds may be used in combination.
The ester used as the solvent in the present invention can be any glycol ester.
Suitable examples of the glycol ester solvents include ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PMA; 2-methoxy-1 -methylethyl acetate; 1-methoxy-2-propyl acetate), dipropylene glycol monomethyl ether acetate, propylene glycol diacetate and the like.
As the glycol ester type solvent, only one kind may be used, or two or more kinds may be used in combination.
In a preferred embodiment of the present invention, the printing medium according to the present invention is characterized in that the organic solvent consist essentially of glycol ether and/or glycol ester. In a preferred embodiment of the present invention, the composition according to the present invention is characterised in that the printing medium comprises at least one glycol ether in an amount of from 5 to 50 wt.-%, preferably 10 to 40 wt.-%, more preferably from 15 to 30 wt.-%, based on the total weight of the printing medium.
In a further preferred embodiment of the present invention, the composition according to the present invention is characterised in that the printing medium comprises at least one glycol ester in an amount of from 10 to 60 wt.-%, preferably 15 to 50 wt.-%, more preferably from 20 to 40 wt.-%, based on the total weight of the printing medium.
The solvent used in the printing medium is preferably predominantly free of aromatics and alkanes.
In the sense of the present invention, predominantly free of aromatics and alkanes means that the printing medium comprises less than 1 wt.-%, preferably less than 0.75 wt.-%, more preferably less than 0.5 wt.-%, more preferably less than 0.25 wt.-%, more preferably less than 0.20 wt.-%, more preferably less than 0.1 wt.-%, aromatics, and alkanes.
Moreover, the printing medium of the present invention comprises preferably a binder. Thereby, it is preferred that the printing medium comprise an acrylic resin as a binder.
Further preferred, the printing medium comprises a copolymer of methyl methacrylate and butyl methacrylate as a binder.
The molecular weight of the binder is not particularly restricted. However, the binder to be used in the printing medium comprises usually a binder with a molecular weight of from 10000 to 250000 g/mol, preferably 20000 to 200000 g/mol, more preferably of from 25000 to 180000 g/mol. The molecular weight is measured by gel permeation chromatography according to DIN 55672-1.
A further suitable binder system is a polyaminoamide. Polyaminoamides are well known epoxide curing agents (publication of Bakelit-AG, page 5, column 3, DE 37 11 947 A1). “Polyaminoamide” is a generic term which describes compounds which contain several free (active) amino groups and at least one amide function per molecule (“International Organisation for Standardisation”). Essentially, they are reaction products of carboxylic acids or their esters with polyamines. Polyaminoamides are obtained primarily from the condensation reaction between a polymeric fatty acid such as a dimeric or trimeric acid, and a polyamine such as e.g. polyethylene polyamine. Examples of these polyaminoamides are described by the following formula
H2N-A-[NH-CO-E-CO-NY-Y-]-NH (1) in which A and Y are the same or different and represent divalent aromatic or aliphatic groups and E represents an aliphatic or aromatic divalent group. This formula only serves as an illustration and does not restrict the class of substances described above which is covered by the scope of the invention. Further examples of the class of compounds are described in detail, for example, in EP 0 654 465 A.
Further suitable binders are polyamide resins. Suitable polyamide resins are those which are used as lacquer resins and hot-melt adhesives. The softening point of the polyamide resins is preferably in the range 50 to 150 °C, in particular in the range 80 to 120 °C. They are generally aliphatic polyamides with structural elements from a dicarboxylic acid and/or a diamine with more than 8 carbon atoms; the dicarboxylic acid components in the polyamides are preferably dimeric fatty acids.
Usually, the printing medium comprises the afore-mentioned binder in an amount of from 10 to 70 wt.-%, preferably 20 to 60 wt.-%, more preferably from 28 to 55 wt.-%, based on the total weight of the printing medium.
In the following, further optional components of the printing medium to be used in the printing medium used in the present invention are described.
That said, the organic printing medium according to the present invention may further comprise at least one additive, selected from the group consisting of a plasticizer, a defoamer, a dispersing agent (or wetting agent), a thixotropic agent or rheology additive and any suitable mixtures thereof.
In case a plasticizer is used in the printing medium, the plasticizer may be present in an amount of from 0.01 to 7 wt.-%, preferably of from 0.5 to 6 wt.-%, more preferably of from 1 to 5 wt.-%, based on the total weight of the printing medium
In case a defoamer is used in the organic printing medium, the defoamer may be comprised in an amount of from 0.01 to 5 wt.-%, preferably of from 0.02 to 2.5 wt.-%, more preferably of from 0.05 to 1 .5 wt.-%, based on the total weight of the printing medium.
The defoamer may be selected from a polysiloxane and/or a silicone oil as a defoamer. Further suitable defoamer (deaerator) are polymer defoamer and mineral oil defoamer which are available for example form the company BYK-Chemie GmbH or from the company Evonik.
In the printing medium used in the present invention, a dispersing agent is preferably used. Dispersing agents in the sense of the present invention are specialized wetting agents that wet out surfaces of particles during the dispersion process, and subsequently stabilize the dispersion such that the particles do not re-agglomerate. Dispersing agents prevent re-agglomeration by either electrostatic stabilization or by steric hindrance. Dispersing agents consist of a polar head that “attaches” to the particle to be dispersed, and a polymer chain that is compatible in the media in which the particle is being dispersed.
In case a dispersing agent is used in the printing medium, the dispersing agent may be comprised, in a first embodiment, in an amount of from 1 to 5 wt.-%, preferably of from 1.25 to 4 wt.-%, more preferably of from 1.5 to 3 wt.-%, based on the total weight of the printing medium.
In case a dispersing agent is used in the printing medium, the dispersing agent may be comprised, in a second embodiment, in an amount of from 0.05 to 15 wt.-%, preferably of from 0.1 to 10 wt.-%, more preferably of from 0.5 to 5 wt.-%, based on the total weight of the printing medium. The dispersing agent may function also as a wetting agent in the printing medium used in the present invention. In the following, the dispersing agent (wetting agent) is described in more detail:
In an embodiment, the dispersing agent is an additive containing groups with affinity for particles. These groups can be selected from the group, consisting of acidic groups, such as carboxylic acids, phosphoric acids; basic groups, such as amines; and neutralized groups or neutral groups. These functional groups can be attached to a low molecular weight resin or polymer with a molecular weight of preferably from 1000 to 5000 g/mol or higher molecular weight resin or polymer (above 5000 g/mol). The resins can be aliphatic, polyester or a polyether. By using an aliphatic resin, a polyester resin or a polyether resin, it is possible to adjust the polarity of the dispersing agent.
In a further embodiment, soy lecithin-based additives and oil-modified polyesters are used as a dispersing agent (wetting agent) in the printing medium used in the present invention.
The composition dispersing agent may be selected further from a polyether phosphate and/or a polyurethane.
Further examples of dispersing agents are amine salts of polyether ester, amine salts of polyether phosphates, aliphatic polycarboxylic acids, amine salts of polyetherester carboxylic acids, anionic surfactants, amine salts of polyetherester/acrylic polymers, and amine salts of polyetherester/acrylic polymers.
Further examples of dispersing agents are fatty acids, phosphonic acid acetates, polyurethanes, polyamines, acrylate polymers and CPT acrylates.
Further examples of dispersing agents are (solutions of) polycarboxylic acid salts of polyamine amides, alkyl ammonium salts of polymeric acid esters, phosphoric acid esters, (solutions of) high molecular weight block copolymer with pigment affine groups, (solutions of) modified polyurethanes, (solutions of) polymeric phosphoric acid ester alkyl ammonium salts, acrylate copolymers with basic, piment-affine groups, block copolymers with pigment affine groups, (solutions of) structured acrylate copolymers with pigment- affine groups and (solutions of) polyacrylates.
Suitable thixotropic agents and rheology additives are, for example, solutions of a modified urea (such as Rheobyk-410), solution of a high molecular weight urea-modified nonpolar polyamide (such as Rheobyk-431), solutions of a modified polyamide (such as Rheobyk-440), micronized, modified, rheological active amide (such as Rheobyk-7503), hydrogenated castor oil, hydrogenated amid-modified hydrogenated castor oil, amides, oxidized polyethylene, poly urea, castor oil, diamond waxes and polyamide waxes, and pyrogenic silica.
The above-described printing medium is preferably composed of components which are non-classified in the Globally Harmonized System of Classification and Labelling of Chemicals (GHS). Therefore, organic solvents as described above are combined with dispersants described above to balance the characteristics of the printing medium as initially discussed and to fulfil, at the same time, the requirement of providing a printing medium being non-classified in the Globally Harmonized System of Classification and Labelling of Chemicals (GHS).
The Globally Harmonized System of Classification and Labelling of Chemicals (GHS) is an internationally agreed-upon standard managed by the United Nations that was set up to replace the assortment of hazardous material classification and labelling schemes previously used around the world.
Core elements of the GHS include standardized hazard testing criteria, universal warning pictograms, and harmonized safety data sheets which provide users of dangerous goods with a host of information. The system acts as a complement to the UN Numbered system of regulated hazardous material transport. Implementation is managed through the UN Secretariat.
Printing mediums used according to the present invention preferably only comprise compounds which fulfil at least one of the following requirements according to the GHS standard: no carcinogen labelling, no mutagenic labelling, no reprotoxic labelling, no sensitization, no skin irritation, not easily flammable, and not causing drowsiness.
In the present invention, it is at first preferred that the organic printing medium is not classified under GHS system for carcinogen labelling, mutagenic labelling and reprotoxic labelling.
In the present invention, it is at second preferred that the organic printing medium is not classified under GHS system for carcinogen labelling, mutagenic labelling, reprotoxic labelling, sensitization labelling, skin irritation labelling and drowsiness labelling.
In the present invention, it is at third preferred that the organic printing medium is not classified under GHS system for carcinogen labelling, mutagenic labelling, reprotoxic labelling, sensitization labelling, skin irritation labelling, drowsiness labelling and flammable labelling.
Printing used mediums according to the present invention preferably only comprise compounds which fulfil at least two, more preferably at least three, more preferably at least four, more preferably at least five, more preferably at least six, more preferably at least seven of the above-mentioned requirements according to the GHS standard.
However, in the most preferred embodiment of the present invention, all compounds to be used in the printing medium do not have any labelling of the GHS system. Regarding the use of the printing medium for indirect printing, the use of components of the printing medium that do not have any labelling is preferred because the printing medium is also used in print shops and printing companies that do not have complete safety devices, such as air outlet apparatuses.
The above-described printing medium which preferably has no GHS labelling provides obviously advantages for the users:
Most of the print shops have extraction systems, but nevertheless small print shops don’t. Such smaller print shops can use the present organic printing medium without any problems.
In addition, using extraction systems is of no use if the substances can be absorbed through the skin. In this case, people have to wear gloves and other suitable protective clothing in case of hazard printing mediums. This requirement can also be avoided by using the above-described printing medium.
Finally, costs for safety expenses can also be reduced, e.g. air exchange rates could be reduced, which saves money in case the printing medium used according to the present invention is applied.
Figure imgf000012_0001
The colour producing inorganic components in the colour pastes may be so called colour frits, i.e. fritted glasses containing colour producing metal oxides and/or inorganic pigments known in the art, provided they are sufficiently stable to stoving. Examples of colour frits include in particular lead borosilicate glasses containing CuO, CoO, MnO, Fe2Oa. Examples of pigments include oxides of the elements Cr, Mn, Fe, Co, Ni, Cu and Cd and their mixed oxides with AI2O3, TiC>2, ZnO, SnC>2, e. g. spinels and titanates; also, sulphides and selenides of Cd, in particular in the form of glazing stable inclusion pigments.
The term "glass flux" is used mainly to denote glass frits which melt at the stoving temperature. Preferred glass frits have a low melting point, e. g. in the region of 450 °C to 800 °C. The melting point and hence the choice of glass depends on the article to be decorated. Borosilicate glasses containing one or more oxides of Li, Na, K, Mg, Ca, Al, Ti, Zr, Sn, Pb, Cd, Sb, Bi are customarily used. A glass flux may also be a combination of SiC>2 or silicates and B2O3 with one or more of the above-mentioned oxides and fluxes such as fluorides, provided that glass formation is possible under the stoving conditions. Further suitable colouring inorganic components to be used in the present invention are described in Ullman’s Encyclopaedia of Technical Chemistry 4th edition, 1977, Volume 14 Ceramic colours to cork; and “Ceramic Glazes. Basics - Properties - Recipes - Application” of Wolf E. Matthes (ISBN 3481296916), both are herewith enclosed by reference.
In a further preferred embodiment, the present invention relates to the use of a composition comprising a. at least one printing medium, comprising a polymeric organic binder system in at least one organic solvent, whereby the printing medium comprises one or more dispersing agents (dispersants, wetting additives), one or more defoamers, one or more binders, optionally one or more plasticizers, one or more solvents and optionally one or more thixotropic agents, whereby the solvent being selected so as to be predominantly free of aromatics and alkanes, the Hansen solubility parameters for the solvent being have a disperse fraction from London interactions (dd) of between 13 and fraction from dipolar inter- actions (dp) of preferably between 1.5 and 8.5 disperse for the hydrogen
Figure imgf000013_0001
bonds (dh) of between 3 and 15 and the evaporation number being between 90
Figure imgf000013_0002
and 600 according to DIN 153 170. In the sense of the present invention, predominantly free of aromatics means that the printing medium comprises less than 1 wt.-%, preferably less than 0.75 wt.-%, more preferably less than 0.5 wt.-%, more preferably less than 0.25 wt.-%, more preferably less than 0.20 wt.-%, more preferably less than 0.1 wt.-%, aromatics, and alkanes.
Use of the compositions
The composition described above is used for the decoration of any suitable substrate, such as substrates selected from glass, porcelain, bone china, enamel and ceramics, by the process of indirect printing.
The present invention is summarised by the following items:
1. Use of a composition, comprising a. at least one printing medium, comprising a polymeric organic binder system in at least one organic solvent for the preparation of decorations on a surface of a substrate by indirect printing, wherein the at least one printing medium has an evaporation number between 80 and 600 according to DIN 153 170.
2. Use according to item 1 , characterized in that the organic solvent comprises an ether and/or ester.
3. Use according to anyone of items 1 or 2, characterized in that the organic solvent comprises glycol ether and/or glycol ester.
4. Use according to anyone of claims 1 to 3, characterized in that the organic solvent consist essentially of glycol ether and/or glycol ester.
5. Use according to anyone of claims 1 to 4, characterised in that the printing medium comprises at least one glycol ether in an amount of from 5 to 50 wt.-%, preferably 10 to 40 wt.-%, more preferably from 15 to 30 wt.-%, based on the total weight of the printing medium.
6. Use according to anyone of items 1 to 5, characterised in that the printing medium comprises at least one glycol ester in an amount of from 10 to 60 wt.-%, preferably 15 to 50 wt.-%, more preferably from 20 to 40 wt.-%, based on the total weight of the printing medium.
7. Use according to anyone of items 1 to 6, characterized in that the printing medium comprises a binder.
8. Use according to anyone of items 1 to 7, characterized in that the printing medium comprise an acrylic resin as a binder.
9. Use according to anyone of items 1 to 8, characterized in that the printing medium comprises a copolymer of methyl methacrylate and butyl methacrylate as a binder.
10. Use according to anyone of items 1 to 9, characterized in that the printing medium comprises a binder with a molecular weight of from 10000 to 250000 g/mol, preferably 20000 to 200000 g/mol, more preferably of from 25000 to 180000 g/mol.
11. Use according to anyone of items 1 to 10, characterized in that the printing medium comprises a binder in an amount of from 10 to 70 wt.-%, preferably 20 to 60 wt.-%, more preferably from 28 to 55 wt.-%, based on the total weight of the printing medium.
12. Use according to anyone of items 1 to 11 , characterized in that the composition further comprises at least one additive, selected from the group consisting of a plasticizer, a defoamer, a dispersing agent, a thixotropic agent or rheology additive and any suitable mixtures thereof.
13. Use according to anyone of items 1 to 12, characterized in that the printing medium comprises a defoamer in an amount of from 0.01 to 5 wt.-%, preferably of from 0.02 to 2.5 wt.-%, more preferably of from 0.05 to 1.5 wt.-%, based on the total weight of the printing medium.
14. Use according to anyone of items 1 to 13, characterized in that the composition further comprises a polysiloxane and/or a silicone oil as a defoamer.
15. Use according to items 1 to 15, characterized in that the printing medium comprises a dispersing agent in an amount of from 0.5 to 5 wt.-%, preferably of from 1.25 to 4 wt.-%, more preferably of from 1.5 to 3 wt.-%, based on the total weight of the printing medium.
16. Use according to anyone of items 1 to 17, characterized in that the composition further comprises a polyether phosphate and a polyurethane as a dispersing agent.
17. Use according to anyone of items 1 to 18, characterized in that the composition further comprises a plasticizer in an amount of from 0.01 to 7 wt.-%, preferably of from 0.5 to 6 wt.-%, more preferably of from 1 to 5 wt.-%, based on the total weight of the printing medium.
18. Use according to anyone of items 1 to 19, characterized in that the composition additionally comprises at least one colouring inorganic component of a stoving-stable pigment and/or a colour frit.
19. Use according to anyone of items 1 to 19, characterized in that the substrate is selected from glass, porcelain, bone china, enamel and ceramics.
Examples
The following organic printing media are prepared by mixing the indicated components at room temperature in the indicated amounts, whereby the solvent is added with the binder under stirring. Thereafter, the plasticizer, the additives and the thixotropic agent are added while stirring. The resulting composition is heated to a temperature of 45 to 75 °C and maintained at this temperature for a period of 30 min to 2 hours. Thereafter, the resulting composition is cooled to room temperature.
Figure imgf000015_0001
One specific formulation is shown below:
Figure imgf000016_0001

Claims

Claims
1. Use of a composition, comprising a. at least one organic printing medium, comprising a polymeric organic binder system in at least one organic solvent, for the preparation of decorations on a surface of a substrate by indirect printing, characterized in that the at least one organic printing medium has an evaporation number between 80 and 600 according to DIN 153 170.
2. Use according to claim 1 , characterized in that the organic solvent comprises glycol ether and/or glycol ester.
3. Use according to claim 1 or 2, characterised in that the printing medium comprises at least one glycol ether in an amount of from 5 to 50 wt.-%, preferably 10 to 40 wt.-%, more preferably from 15 to 30 wt.-%, based on the total weight of the printing medium.
4. Use according to anyone of claims 1 to 3, characterised in that the printing medium comprises at least one glycol ester in an amount of from 5 to 60 wt.-%, preferably 15 to 50 wt.-%, more preferably from 20 to 40 wt.-%, based on the total weight of the printing medium.
5. Use according to anyone of claims 1 to 4, characterized in that the printing medium comprises a binder.
6. Use according to anyone of claims 1 to 5, characterized in that the printing medium comprises acrylic resin as a binder.
7. Use according to anyone of claims 1 to 6, characterized in that the printing medium comprise a copolymer of methyl methacrylate and butyl methacrylate as a binder.
8. Use according to anyone of claims 1 to 7, characterized in that the printing medium comprises a binder with a molecular weight of from 10000 to 250000 g/mol, preferably 20000 to 200000 g/mol, more preferably of from 25000 to 180000 g/mol.
9. Use according to anyone of claims 1 to 8, characterized in that the printing medium comprises a binder in an amount of from 10 to 70 wt.-%, preferably 20 to 60 wt.-%, more preferably from 28 to 55 wt.-%, based on the total weight of the printing medium.
10. Use according to anyone of claims 1 to 9, characterized in that the composition further comprises at least one additive, selected from the group consisting of a plasticizer, a defoamer, a dispersing agent, a thixotropic agent and any suitable mixtures thereof. Use according to anyone of claims 1 to 10, characterized in that the printing medium comprises a defoamer in an amount of from 0.01 to 5 wt.-%, preferably of from 0.02 to 2,5 wt.-%, more preferably of from 0.05 to 1 .5 wt.-%, based on the total weight of the printing medium. Use according to anyone of claims 1 to 11 , characterized in that the composition further comprises a polysiloxane and a silicone oil as a defoamer. Use according to claims 1 to 12, characterized in that the printing medium comprises a dispersing agent in an amount of from 0.5 to 5 wt.-%, preferably of from 1. ,25 to 4 wt.-%, more preferably of from 1.5 to 3 wt.-%, based on the total weight of the printing medium. Use according to anyone of claims 1 to 13, characterized in that the composition further comprises a polyether phosphate and/or polyurethane as a dispersing agent. Use according to anyone of claims 1 to 14, characterized in that the composition further comprises a plasticizer in an amount of from 0.01 to 7 wt.-%, preferably of from 0.5 to 6 wt.-%, more preferably of from 1 to 5 wt.-%, based on the total weight of the printing medium. Use according to anyone of claims 1 to 15, characterized in that the composition additionally comprises b. at least one colouring inorganic component of a stoving-stable pigment and/or a colour frit. Use according to anyone of claims 1 to 16 for the decoration of a substrate selected from glass, porcelain, bone china, enamel and ceramics. Use according to anyone of claims 1 to 17 that the medium has no GHS labeling. Use according to anyone of claims 1 to 18 that the medium comprises a polymeric organic binder system in at least one organic solvent, whereby the printing medium comprises one or more dispersing agents, one or more defoamers, one or more binders, optionally one or more plasticizers, one or more solvents and optionally one or more thixotropic agents, whereby the solvent being selected so as to be predominantly free of aromatics and alkanes, the Hansen solubility parameters for the solvent having a disperse fraction from London interactions (dd) of between 13 and 17 , a fraction from dipolar interactions (dp) of pref
Figure imgf000018_0001
erably between 1.5 and 8.5 and a disperse for the hydrogen bonds (dh)
Figure imgf000018_0002
of between 3 and 15 and the evaporation number being between 80 and
Figure imgf000018_0003
18
600 according to DIN 153 170.
PCT/EP2022/084711 2021-12-08 2022-12-07 Environmentally friendly medium for ceramic colours for indirect decoration of glass, porcelain, bone china, enamel, and ceramics WO2023104849A1 (en)

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