CN1039702C - Cover-coat for colour on glazed ceramics and process and product thereof - Google Patents
Cover-coat for colour on glazed ceramics and process and product thereof Download PDFInfo
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- CN1039702C CN1039702C CN 93110379 CN93110379A CN1039702C CN 1039702 C CN1039702 C CN 1039702C CN 93110379 CN93110379 CN 93110379 CN 93110379 A CN93110379 A CN 93110379A CN 1039702 C CN1039702 C CN 1039702C
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- colour
- cover
- cover layer
- coat
- glazed ceramics
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Abstract
The present invention relates to a paint applying cover layer of ceramic glaze, a processing decoration method thereof and a product, and belongs to decoration and protection of ceramic glaze applying surfaces. The cover layer material of the present invention is prepared from 84% to 93% of PbO-B2O3-SiO2, 3.45% to 9.63% of Al2O3 and 2% to 7% of coloration auxiliary agent which is selected from ZnO, TiO2 and SnO2, wherein the PbO-B2O3-SiO2 is used as a main constituent. The raw materials of the cover layer are blended, are melted at the temperature of 1300 to 1350DEGC, are quenched by water, and are ground into powder. The cover layer powder is mixed with oil, is printed on the printed stained paper, is pasted on ceramics, and is fired once. The product of the present invention can reduce the lead release quantity below 0.3 mg/dm<2>, and maintains the good characteristics of lead pigments, and the picture is vivid and undistorted.
Description
The present invention relates to a kind of cover-coat for colour on glazed ceramics and processing decoration method.It belongs to the decoration and the protection on ceramic over-glaze decoration surface, and it comprises the composition and the processing decoration method of cover-coat for colour on glazed ceramics.
At present, the flux that is adopted in ceramic industry all contains plumbous oxide (PbO).Because this oxide compound can make flux meltable and the melt temperature scope of broad arranged, can improve the refractive index and the elasticity of glass, can make pigment colour adopt more horn of plenty, can also slow down alkalimetal ion dissociating in glass, have and the matched thermal expansivity of most of enamel.Therefore in colour on glazed ceramics, also can't do without this component of plumbous oxide from ancient times to the present.But other metal oxide in plumbiferous compound and the colour on glazed ceramics and the compound of cadmium etc. all are deleterious, especially with the tableware of over-glaze pigment decoration, drinking utensils, tea set etc. are in environment for use, poisonous components such as lead, cadmium can weather and stripping, harm people's health.This has just proposed a premium properties that should keep leaded over-glaze pigment, reduces the research topic of plumbous quantity of cadmium release again as far as possible.In recent years, it is more to be engaged in the department of development " colorant on the acidproof leadless glaze ", " the unleaded flux of ceramic pigment on the glaze ".
Chinese patent application numbers 911016120 discloses a kind of glass composition, and its purpose provides a kind of unleaded surrogate, and its formation is:
Silicon-dioxide 38-50%
Zirconium white 9-17%
Boron oxide 26-50%
Sodium oxide or (with) oxidation first 4-15%
Lithium Oxide 98min 2-8%
Titanium oxide 0-15%
Aluminum oxide 0-15%
Stannic oxide 0-10%
Cerium oxide 0-10%
Magnesium oxide 0-10%
Zinc oxide 0-10%
Bismuth oxide 0-8%
Calcium oxide 0-5%
Plumbous oxide 0-5%
The glass flux composition that fluorochemical 0-2% forms in order to constitute a kind of enamel composition, is applied to them on goods that burnt till, and twice firing plays the decoration provide protection.Its weak point is:
The a chemical stability is bad, low in glossiness;
B can influence the colour generation of some color to the paint color bad adaptability, causes aberration big, makes the original picture distortion;
The c thermal expansivity is big, easily causes picture crackle or burst porcelain;
The d twice firing, complex process;
E is owing to contain a large amount of ZrO in the component
2, cause the glass milkiness transparency bad.
F is only limited to and is used for leadless glaze.
The objective of the invention is to avoid above-mentioned weak point of the prior art and a kind of premium properties that can keep ceramic leaded over-glaze pigment fully is provided, can reduces the plumbous quantity of cadmium release of picture on the glaze greatly, suitable picture cracking, the ideal cover-coat for colour on glazed ceramics that the water white transparency light is firm of can not causing of, thermal expansivity very little to all pigment colour generation influences.
The present invention also aims to provide a kind of once-firing method of very easy processing decoration cover layer and decorate the various ceramics of protection, thereby thoroughly avoided the harm that all pigment may bring on the picture on the glaze with this method.
Purpose of the present invention can reach by following measure:
Cover-coat for colour on glazed ceramics material of the present invention constitutes (wt%) by following component:
A, by PbO, B
2O
3, SiO
2The main body composition of forming 84.0～93.0
B, with Al
2O
3It is main viscosity modifier 3.45～9.63;
C, from ZnO, TiO
2, SnO
2In at least a colour generation auxiliary agent 2.0～7.0 that chooses.
The key problem in technology of cover-coat for colour on glazed ceramics prescription of the present invention is to make it to have suitable thermal expansivity and to the high-fidelity performance of all various pigment colour generations.
PbO-B
2O
3-SiO
2The stabilizing network structure of system is given the high glossiness of glass, wide melt temperature scope, lower thermal expansivity and high chemical stability, PbO and the B in the main body composition in addition
2O
3Colour generation to pigment has outstanding contributions.The unleaded flux of these premium propertiess is difficult to reach.
Viscosity modifier is the indispensable important component of the present invention, and is because suitable cover layer viscosity can guarantee that picture pigment does not fade in roasting burning process, especially particularly evident for the iron oxide red picture effect that easily fades.
The cover layer is introduced from ZnO, B in forming
2O
3, SnO
2In the colour generation auxiliary agent that chooses yes helps the colour generation of shades of colour in sintering process, particularly help gold size and grow up and make its colour generation pure for the gold thread picture.Their adding simultaneously makes that also glass structure is more form compact and stable, has reduced plumbous quantity of cadmium release to greatest extent.
Why the present invention does not introduce basic metal of the prior art and alkaline earth metal oxide, is because their affiliation that adds increases the thermal expansivity that covers layer, causes the picture cracking, even can cause burst porcelain.
The compositing range following (wt%) of each concrete component in above-mentioned a, b, the c three big components in cover-coat for colour on glazed ceramics prescription of the present invention:
PbO 24.15～48.93
B
2O
3 4.05～14.08
SiO
2 31.65～52.50
Al
2O
3 3.45～9.63
SnO
2 0～2.90
TiO
2 0～2.48
ZnO 0～4.43
The processing decoration method of cover-coat for colour on glazed ceramics of the present invention is characterized in that comprising the steps:
A, according to a following component and proportioning preparation cover layer powder (wt%):
PbO 24.15～48.93
B
2O
3 4.05～14.08
SiO
2 31.65～52.50
Al
2O
3 3.45～9.63
SnO
2 0～2.90
TiO
2 0～2.48
ZnO 0～4.43
SnO wherein
2, TiO
2, three kinds of colour generation auxiliary agents of ZnO use a kind of at least;
B, will cover the layer powder be printed onto on the marble paper of pattern out of the press;
C, the marble paper that will be printed on cover layer are attached to the ceramic last time that desire decorates and burn till.
The processing decoration method of cover-coat for colour on glazed ceramics of the present invention, wherein the preparation procedure of processing of cover layer powder comprises:
A, cover layer feed proportioning mixing;
B, 1300～1350 ℃ of fusion half an hour;
C, in cold water, quench broken;
D, be ground to 90% particle and reach 5 μ m;
E, discharging, dry for standby.
The cover layer powder of oven dry allocated with silk screen printing oil, and material oil prints additional one deck cover layer with 1: 0.8～1.0 on silk screen marble paper out of the press, just become to have the marble paper that covers layer material.
As marble paper on the common glaze, the marble paper that will have the cover layer is attached on the ceramic of desire decoration.Bake burning down and be incubated ten minutes at 800 ℃～850 ℃, bake about 3 hours time, once can burn till the ceramic that has the protective guard layer.
Can decorate the ceramic of the useful over-glaze pigment decoration of protection institute with the processing decoration method of cover-coat for colour on glazed ceramics material of the present invention and cover-coat for colour on glazed ceramics of the present invention; the decoration that is particularly useful for the ceramic of cooker, tableware, kitchenware, the goods picture lead release behind the Decorative Cover layer is less than 0.3mg/dm
2, quantity of cadmium release is less than 0.01mg/dm
2And protected the original picture color.
The present invention will now be further detailed embodiment:
Table I: the component of embodiment 1～embodiment 8 cover-coat for colour on glazed ceramics and ratio of components (wt%).
Table II: with the same color of colour on glazed ceramics decoration and the model of same picture, respectively behind the cover layer processing decoration made from the prescription of the embodiment 1～embodiment 8 shown in the Table I with covering layer model not, record lead/quantity of cadmium release mg/dm according to the method for ZBY24006-89
2Synopsis.
Table III, the same color of decorating with colour on glazed ceramics and the model of same picture, record with the color colour-difference meter behind the cover layer processing decoration made from the prescription of the embodiment 1～embodiment 8 shown in the Table I respectively with the aberration synopsis that does not cover model.
Table I embodiment 1-8 prepare burden (wt%)
Table II embodiment 1-8 lead/quantity of cadmium release (mg/dm
2)
Table III embodiment 1-8 with do not cover sample aberration Δ E
The present invention has following advantage compared to existing technology:
1, to reducing ceramic glazing dyestuff Lead and cadmium amount remarkable result is arranged, lead release can be reduced to 0.3mg/dm2, quantity of cadmium release can be reduced to 0.10mg/dm2 And glossiness Height, chemical stability is good, not only reduces Lead and cadmium, and to other elements in the pigment Poison and also play protective action.
2, good to paint color adaptability, the transparency height, aberration is little, thereby makes various face Material is colour generation well, comprises iron oxide red and golden red, does not make the original picture distortion.
3, thermal coefficient of expansion is lower, can not cause picture crackle or burst porcelain.
4, once-firing has been simplified technology.
5, the wearing and tearing of picture on the glaze have been avoided.
Claims (5)
1, a kind of cover-coat for colour on glazed ceramics is characterized in that constituting (wt%) by following three big components:
A, by PbO, B
2O
3, SiO
2The main body component of forming 84.0～93.0;
B, with Al
2O
3It is main viscosity modifier 3.45～9.63;
C, from ZnO, TiO
2, SnO
2In at least a colour generation auxiliary agent 2.0～7.0 that chooses;
The compositing range following (wt%) of each concrete component in the above-mentioned three big components in the cover-coat for colour on glazed ceramics prescription:
PhO 24.15～48.93
B
2O
3 4.05～14.08
SiO
2 31.65～52.50
Al
2O
3 3.45～9.63
SnO
2 0～2.90
TiO
2 0～2.48
ZnO 0～4.43
2, a kind of processing decoration method of cover-coat for colour on glazed ceramics is characterized in that comprising the steps:
A, according to a following component and proportioning preparation cover layer powder (wt%):
PbO 24.15～48.93
B
2O
3 4.05～14.08
SiO
2 31.65～52.50
Al
2O
3 3.45～9.63
SnO
2 0～2.90
TiO
2 0～2.48
ZnO 0～4.43
SnO wherein
2, TiO
2, three kinds of colour generation auxiliary agents of ZnO use a kind of at least;
B, will cover the layer powder be printed onto on the marble paper of pattern out of the press;
C, the marble paper that will be printed on cover layer are attached to the ceramic last time that desire decorates and burn till.
3,, it is characterized in that the step for preparing cover layer powder comprises according to the processing decoration method of the described cover-coat for colour on glazed ceramics of claim 2:
A, cover layer feed proportioning mixing;
B, 1300～1350 ℃ of fusion half an hour;
C, in cold water, quench broken;
D, be ground to 90% particle and reach 5 μ m;
E, discharging, oven dry.
4, according to the processing decoration method of the described cover-coat for colour on glazed ceramics of claim 2, when its special sheet was silk screen printing, the ratio of cover layer powder and off-set oil was good with 1: 0.8～1.0.
5, according to the processing decoration method of the described cover-coat for colour on glazed ceramics of claim 2, its special sheet is and will is with the marble paper at the cover layer to be attached on the ceramic of desire decoration that bake baking down and be incubated ten minutes at 800 ℃～850 ℃, firing time is about 3 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93110379 CN1039702C (en) | 1993-04-14 | 1993-04-14 | Cover-coat for colour on glazed ceramics and process and product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93110379 CN1039702C (en) | 1993-04-14 | 1993-04-14 | Cover-coat for colour on glazed ceramics and process and product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1093684A CN1093684A (en) | 1994-10-19 |
| CN1039702C true CN1039702C (en) | 1998-09-09 |
Family
ID=4988252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93110379 Expired - Fee Related CN1039702C (en) | 1993-04-14 | 1993-04-14 | Cover-coat for colour on glazed ceramics and process and product thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1039702C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1911685B (en) * | 2005-08-10 | 2010-04-28 | 杨曙光 | Manufacturing technology of ink and wash ceramic drawing |
| CN102731145A (en) * | 2012-06-14 | 2012-10-17 | 卡罗比亚釉料（昆山）有限公司 | Color changeable ceramic glaze for preparing ceramic |
| CN102731151A (en) * | 2012-06-14 | 2012-10-17 | 卡罗比亚釉料（昆山）有限公司 | Leadless color ceramic glaze |
| CN110713345B (en) * | 2019-12-11 | 2020-04-10 | 佛山市天工嘉荟文化科技有限公司 | Enamel color material, preparation method and application in repairing enamel cultural relics painted on porcelain body |
| CN115611518A (en) * | 2022-10-31 | 2023-01-17 | 安徽昆仑新材料科技有限公司 | Environment-friendly ceramic glaze with anti-freezing and anti-cracking effects and preparation method thereof |
-
1993
- 1993-04-14 CN CN 93110379 patent/CN1039702C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1093684A (en) | 1994-10-19 |
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