WO2006099950A1 - Process for producing dishwasher-resistant, scratch- and abrasion-resistant precious metal decorations - Google Patents

Process for producing dishwasher-resistant, scratch- and abrasion-resistant precious metal decorations Download PDF

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Publication number
WO2006099950A1
WO2006099950A1 PCT/EP2006/002147 EP2006002147W WO2006099950A1 WO 2006099950 A1 WO2006099950 A1 WO 2006099950A1 EP 2006002147 W EP2006002147 W EP 2006002147W WO 2006099950 A1 WO2006099950 A1 WO 2006099950A1
Authority
WO
WIPO (PCT)
Prior art keywords
flux
precious metal
process according
siliceous
resistant
Prior art date
Application number
PCT/EP2006/002147
Other languages
French (fr)
Inventor
Lutz Poth
Jean-Claude Guichard
Heinz Wolfgang Augustin
Original Assignee
Ferro Gmbh
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 Ferro Gmbh filed Critical Ferro Gmbh
Priority to EP06723301A priority Critical patent/EP1863746A1/en
Publication of WO2006099950A1 publication Critical patent/WO2006099950A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/4505—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application
    • C04B41/4511—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application using temporarily supports, e.g. decalcomania transfers or mould surfaces
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
    • C04B41/90—Coating or impregnation for obtaining at least two superposed coatings having different compositions at least one coating being a metal

Definitions

  • the present invention concerns a process for producing dishwasher-resistant, scratch- and abrasion-resistant precious metal decorations on substrates, in particular siliceous substrates, wherein a bright precious metal preparation is applied first, followed on top by a finely- ground siliceous flux to which a screen-printing medium has been added.
  • the invention also concerns the decorated substrate obtainable with the process.
  • Patent specification DE 3122546 describes the use of a lead borosilicate-containing glass frit to produce ceramic transfers, this glass frit being positioned as an underlay between the bright precious metal preparation and the support. A matt precious metal decoration can be obtained in this way with a single firing, but it is not scratch- or abrasion-resistant .
  • Patent specification DE 3524912 describes the use of a lead-containing glass frit to produce scratch- and abrasion-resistant precious metal decorations, wherein a bright precious metal preparation is applied first, followed on top by a siliceous flux. The flux and the precious metal decoration are fired simultaneously.
  • the flux described in DE 3524912 is based on a borosilicate frit, which has a high lead content and contains 30 to 80% lead oxide.
  • DE 3616547 describes the production of a ceramic transfer, consisting of a support, an image layer made from a thermoplastic bright gold preparation, a second layer containing a colourless lead borosilicate glaze frit and a final top coat based on acrylate resin.
  • the object of the present invention is therefore to provide an environmentally friendly process for producing precious metal decorations on substrates, which produces dishwasher- resistant, scratch- and abrasion-resistant precious metal decorations . This object is achieved with a process according to claim 1.
  • these two frits can be mixed in any proportions, in order to establish the necessary softening range for the particular firing condition.
  • the siliceous flux can also be applied below the bright precious metal layer to produce a silk matt precious metal decoration.
  • the flux layer lying beneath the precious metal layer is applied in a manner such that a pattern is formed.
  • the invention also concerns the decorated substrates which have been produced by the processes described above.
  • Example 1 The invention is explained in more detail below by means of the examples, which do not restrict the invention.
  • Example 1 The invention is explained in more detail below by means of the examples, which do not restrict the invention.
  • Example 1 Example 1 :
  • the transfer is transferred to a porcelain plate and this is cold-to-cold fired at 880 0 C for 75 minutes.
  • the precious metal decoration obtained has an attractive silk matt gloss and has outstanding scratch resistance and dishwasher resistance.
  • the entire decoration is film-coated with a commercial film solution (80 450 from Ferro GmbH) using a printing screen made from polyester fabric with 27 threads/cm. After the film solution has dried, the transfer is transferred to a bone china plate and this is cold-to-cold fired at 820 0 C for 150 minutes.
  • a commercial film solution 80 450 from Ferro GmbH
  • the precious metal decoration obtained has an attractive silk matt gloss and has outstanding scratch resistance and dishwasher resistance.

Abstract

The present invention concerns a process for producing dishwasher-resistant, scratch- and abrasion-resistant precious metal decorations on substrates, in particular siliceous substrates, wherein a bright precious metal preparation is applied first, followed on top by a finely ground siliceous flux to which a screen-printing medium has been added. The invention also concerns the decorated substrate obtainable with the process.

Description

Process for producing dishwasher-resistant, scratch- and abrasion-resistant precious metal decorations
Description
The present invention concerns a process for producing dishwasher-resistant, scratch- and abrasion-resistant precious metal decorations on substrates, in particular siliceous substrates, wherein a bright precious metal preparation is applied first, followed on top by a finely- ground siliceous flux to which a screen-printing medium has been added. The invention also concerns the decorated substrate obtainable with the process.
Gold decorations on siliceous surfaces, such as porcelain, bone china, earthenware, tiles, enamel or glass, commonly exhibit only low abrasion and scratch resistance. In addition, the dishwasher resistance of precious metal decorations is frequently not adequate to cope with the high demands placed on hotel and catering crockery, so that the use of precious metal decorations is often avoided in these sectors. On tiles too, the direct application of precious metal decorations is frequently avoided, since the precious metal coating does not withstand repeated stress, e.g. from scouring grit.
It is possible to melt a transparent flux onto a pre-fired precious metal decoration in a further firing. This flux- covered precious metal decoration is scratch-resistant and has a high chemical resistance. This process is used, but it is very laborious, since a second printing is necessary, in which the flux must be applied exactly on top of the fired precious metal decoration and a new firing is required.
In the tile sector, a process is used in which a pre-fired precious metal decoration is then scattered with glass granules (Vetrosa) , which are melted in a subsequent firing at a lower firing temperature. The molten glass covers the precious metal decorative coating and makes it highly resistant to abrasion. In this case too a time-consuming second firing is necessary. Attempts to achieve such decorations in a single firing show that this is only possible if pastes having a high precious metal content (e.g. gold content 38%) are used, which are too expensive for the manufacture of tiles, however.
A process in which in a first firing a bright precious metal coating is fired onto the substrate, this then being covered with a glass frit, which is melted onto the precious metal decoration in a second firing stage, is described in DE 1233769. The need for a second firing stage in this process is time-consuming and expensive, so this process is rarely used.
Patent specification DE 3122546 describes the use of a lead borosilicate-containing glass frit to produce ceramic transfers, this glass frit being positioned as an underlay between the bright precious metal preparation and the support. A matt precious metal decoration can be obtained in this way with a single firing, but it is not scratch- or abrasion-resistant . Patent specification DE 3524912 describes the use of a lead-containing glass frit to produce scratch- and abrasion-resistant precious metal decorations, wherein a bright precious metal preparation is applied first, followed on top by a siliceous flux. The flux and the precious metal decoration are fired simultaneously. The flux described in DE 3524912 is based on a borosilicate frit, which has a high lead content and contains 30 to 80% lead oxide.
DE 3616547 describes the production of a ceramic transfer, consisting of a support, an image layer made from a thermoplastic bright gold preparation, a second layer containing a colourless lead borosilicate glaze frit and a final top coat based on acrylate resin.
When the transfer having the above structure is fired, a precious metal decoration coated with a glaze layer is obtained which is particularly abrasion- and scratch- resistant. In addition to other metal oxides, the glaze frit described in DE 3616547 contains as a substantial constituent lead oxide in a proportion of 20 to 55 wt . % .
Due to the toxic effect of lead compounds, the use of such fluxes having a high lead content for the decoration of utility ware is virtually unacceptable nowadays.
The object of the present invention is therefore to provide an environmentally friendly process for producing precious metal decorations on substrates, which produces dishwasher- resistant, scratch- and abrasion-resistant precious metal decorations . This object is achieved with a process according to claim 1.
A process is provided for the production of dishwasher- resistant, scratch- and abrasion-resistant precious metal decorations on substrates, in particular siliceous substrates, wherein a bright precious metal preparation is applied first, followed on top by a finely ground siliceous flux to which a screen printing medium has been added, which is characterised in that the siliceous flux is free from lead and cadmium and the bright precious metal preparation is fired together with the flux in one firing at 500 to 1000°C.
The application can be made directly or with the aid of an intermediate support (e.g. transfer process).
Glass frits with a high lead content have an inherently low softening point and are therefore particularly suitable for forming well fused and closed glass layers, even at varying firing temperatures, which adequately protect a precious metal decoration beneath them. On the other hand, due to their low softening point, lead-containing glass frits tend to form an undulating surface at elevated firing temperatures, such that the bright precious metals coated with flux commonly have an uneven appearance .
Surprisingly it has now been found that with the use according to the invention of fluxes having a small particle size, adequately homogeneous coatings on top of the precious metal decoration can be obtained, even with lead-free fluxes. Experience has shown that it is advantageous if the siliceous flux has a particle size of d90 < 20 μm and preferably a particle size of d90 < 15 μm.
The known bright gold, bright platinum and bright palladium preparations suitable for screen printing, and in particular for the production of transfers, can be used as bright precious metal preparations. Such bright gold preparations generally consist of one or more organic precious metal compounds having a total precious metal content of 6 to 16%, a flux consisting of non-precious metal compounds, a binder and an organic solvent blend. Appropriate additives to improve the rheology can be used to establish the desired printing properties.
It has been found that depending on the desired firing temperature, different frit compositions are particularly suitable .
At low firing temperatures a frit having an initial softening temperature below 7000C and a hemisphere temperature of over 8000C and having the following composition has proved effective as the glass frit:
20-40% B2O3
30-50% SiO2
5-20% Al2O3
0-10% BaO
0-10% CaO
0-5% MgO
0-3% K2O
0-3% Li2O
0-3% ZnO
preferably with the following composition of the low- melting frit:
Glass flux LM:
29 .8% B2O3
36 .2% SiO2
12 .3% Al2O3
7 .7% BaO
5 .1% CaO
2 .8% MgO
2 .1% K2O
1 5% Li2O
2 .2% ZnO
This frit has an initial softening point of 6900C, a hemisphere temperature of 8200C and a coefficient of thermal expansion of 61 x 10"7/K. At high firing temperatures a frit having an initial softening temperature above 7000C and a hemisphere temperature of over 10000C and having the following composition has proved effective as the glass frit:
5-20% B2O3
60-80% SiO2
0-10% Al2O3
0-3% BaO
0-3% CaO
0-10% Na2O
preferably with the following composition of the high- melting frit :
Glass flux HM:
10.5% B2O3
75% SiO2
5.0% Al2O3
1.0% BaO
1.5% CaO
7% Na2O
This frit has an initial softening point of 7600C, a hemisphere temperature of 112O0C and a coefficient of thermal expansion of 50 x 10"7/K.
By using two glass frits with different softening points and mixtures thereof, the softening range of the coating flux can be adjusted according to the firing conditions and to the substrate to be decorated. This coating flux system can therefore be used within a broad firing range. The coefficient of thermal expansion of the flux coating can also be adjusted to the particular substrate by using an appropriate mixture of two glass frits having different softening ranges .
Depending on the chosen firing temperature, these two frits can be mixed in any proportions, in order to establish the necessary softening range for the particular firing condition.
In addition, the siliceous flux can also be applied below the bright precious metal layer to produce a silk matt precious metal decoration. In this case the flux layer lying beneath the precious metal layer is applied in a manner such that a pattern is formed.
To obtain the desired decoration, one or more ceramic decoration colours can be applied in addition to the bright precious metal preparation. These are commercial decoration colours such as those from the Samba range produced by Ferro GmbH. Examples which are cited here are the lead-free colours 111650 (green) , 141650 (black) and 771630 (purple) .
The invention also concerns the decorated substrates which have been produced by the processes described above.
The invention is explained in more detail below by means of the examples, which do not restrict the invention. Example 1 :
To produce a transfer, a commercial bright gold preparation in paste form (GG 5566 10 from Ferro GmbH with a gold content of 10 wt.%) is printed onto a dextrin-coated backing paper using a printing screen made from polyester fabric with 120 threads/cm. The low-melting flux Glass flux LM is pasted in the pasting ratio 10:10 with a commercial screen printing medium (80 595 from Ferro GmbH, methacrylate polymer and plasticiser dissolved in aromatic solvents) . After the bright gold paste has dried, it is overprinted with the pasted Glass flux LM. A printing screen made from polyester fabric with 140 threads/cm is used for this. Then, after the flux overprint has dried, the entire decoration is film-coated with a commercial film solution (80 450 from Ferro GmbH, methacrylate polymer and plasticiser dissolved in aromatic solvents) using a printing screen made from polyester fabric with 27 threads/cm. After the film solution has dried, the transfer is transferred to a porcelain plate and this is cold-to- cold fired at 8000C for 4 hours.
The precious metal decoration obtained has an attractive silk matt gloss and has outstanding scratch resistance and dishwasher resistance.
Example 2 :
To produce a transfer, a commercial bright gold preparation in paste form (GG 5566 10 from Ferro GmbH) is printed onto a dextrin-coated backing paper using a printing screen made from polyester fabric with 120 threads/cm. The high-melting flux Glass flux HM is pasted in the pasting ratio 10:10 with a commercial screen printing medium (80 595 from Ferro GmbH) . After the bright gold paste has dried, it is overprinted with the pasted Glass flux HM. A printing screen made from polyester fabric with 73 threads/cm is used for this. Then, after the flux overprint has dried, the entire decoration is film-coated with a commercial film solution (80 450 from Ferro GmbH) using a printing screen made from polyester fabric with 27 threads/cm.
After the film solution has dried, the transfer is transferred to a porcelain plate and this is cold-to-cold fired at 8800C for 75 minutes.
The precious metal decoration obtained has an attractive silk matt gloss and has outstanding scratch resistance and dishwasher resistance.
Example 3 :
To produce a transfer, a commercial bright gold preparation in paste form (GG 5566 10 from Ferro GmbH) is printed onto a dextrin-coated backing paper using a printing screen made from polyester fabric with 120 threads/cm. A 1:1 mixture of the high-melting flux Glass flux HM and the low-melting flux Glass flux LM is pasted in the pasting ratio 10:10 with a commercial screen printing medium (80 505 from Ferro GmbH) . After the bright gold paste has dried, it is overprinted with the pasted glass flux mixture. A printing screen made from polyester fabric with 73 threads/cm is used for this. Then, after the flux overprint has dried, the entire decoration is film-coated with a commercial film solution (80 450 from Ferro GmbH) using a printing screen made from polyester fabric with 27 threads/cm. After the film solution has dried, the transfer is transferred to a bone china plate and this is cold-to-cold fired at 8200C for 150 minutes.
The precious metal decoration obtained has an attractive silk matt gloss and has outstanding scratch resistance and dishwasher resistance.

Claims

Cl aims
1. Process for producing dishwasher-resistant, scratch- and abrasion-resistant precious metal decorations on substrates, in particular siliceous substrates, wherein a bright precious metal preparation is applied first, followed on top by a finely ground siliceous flux to which a screen printing medium has been added, characterised in that the siliceous flux is free from lead and cadmium and the bright precious metal preparation is fired together with the flux in one firing at 500 to 10000C.
2. Process according to claim 1, characterised in that the siliceous flux has a particle size d90 < 20 μm and preferably a particle size d90 < 15 μm.
3. Process according to claims 1 to 2 , characterised in that the siliceous flux is a low-melting flux with an initial softening point below 7000C.
4. Process according to claim 3, characterised in that the low-melting flux is selected from the composition: 20-40% B2O3
30-50% SiO2
5-20% Al2O3
0-10% BaO
0-10% CaO
0-5% MgO
0-3% K2O
0-3% Li2O
0-3% ZnO
5. Process according to claims 1 to 2 , characterised in that the siliceous flux is a high-melting flux with an initial softening point above 7000C.
6. Process according to claim 5, characterised in that the high-melting flux is selected from the composition:
5-20% B2O3
60-80% SiO2
0-10% Al2O3
0-3% BaO
0-3% CaO
0-10% Na2O
7. Process according to claims 1 to 6, characterised in that the siliceous flux is a mixture of the low-melting and high-melting flux.
8. Process according to claim 7, characterised in that the two fluxes used have different coefficients of thermal expansion.
9. Process according to claims 1 to 8 , characterised in that the siliceous flux is also applied below the bright precious metal layer.
10. Process according to claim 9, characterised in that the flux layer lying beneath the precious metal layer is applied in a manner such that a pattern is formed.
11. Process according to claims 1 to 10, characterised in that in addition to the bright precious metal preparation, one or more ceramic decoration colours are applied beneath the siliceous flux.
12. Decorated substrate, produced by a process according to claims 1 to 11.
PCT/EP2006/002147 2005-03-24 2006-03-08 Process for producing dishwasher-resistant, scratch- and abrasion-resistant precious metal decorations WO2006099950A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP06723301A EP1863746A1 (en) 2005-03-24 2006-03-08 Process for producing dishwasher-resistant, scratch- and abrasion-resistant precious metal decorations

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005013866.7 2005-03-24
DE200510013866 DE102005013866A1 (en) 2005-03-24 2005-03-24 Process for producing dishwasher-resistant, scratch-resistant and abrasion-resistant precious metal decorations

Publications (1)

Publication Number Publication Date
WO2006099950A1 true WO2006099950A1 (en) 2006-09-28

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ID=36499042

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Application Number Title Priority Date Filing Date
PCT/EP2006/002147 WO2006099950A1 (en) 2005-03-24 2006-03-08 Process for producing dishwasher-resistant, scratch- and abrasion-resistant precious metal decorations

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DE (1) DE102005013866A1 (en)
WO (1) WO2006099950A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102050560B (en) * 2009-11-06 2013-04-03 湖北新华光信息材料有限公司 Method for preparing low-melting glass clinkers
CN105837027A (en) * 2016-03-28 2016-08-10 伍治东 Preparation process of tempered glass with surface being coated with copper-based composite coating

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995009823A1 (en) * 1993-10-02 1995-04-13 Cookson Matthey Ceramics Plc Frit-containing composition
DE19937388A1 (en) * 1999-08-07 2001-02-08 Dmc2 Degussa Metals Catalysts Precious metal decoration matting composition, especially for producing matt gold decorations on porcelain, ceramic or glass, contains a non-softening titanium dioxide-free oxidic and-or silicate matting agent

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995009823A1 (en) * 1993-10-02 1995-04-13 Cookson Matthey Ceramics Plc Frit-containing composition
DE19937388A1 (en) * 1999-08-07 2001-02-08 Dmc2 Degussa Metals Catalysts Precious metal decoration matting composition, especially for producing matt gold decorations on porcelain, ceramic or glass, contains a non-softening titanium dioxide-free oxidic and-or silicate matting agent

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102050560B (en) * 2009-11-06 2013-04-03 湖北新华光信息材料有限公司 Method for preparing low-melting glass clinkers
CN105837027A (en) * 2016-03-28 2016-08-10 伍治东 Preparation process of tempered glass with surface being coated with copper-based composite coating

Also Published As

Publication number Publication date
EP1863746A1 (en) 2007-12-12
DE102005013866A1 (en) 2006-09-28

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