CN101050059B - Covering layer without lead, cadmium of pigment without lead on ceramic glaze, and preparation method - Google Patents

Covering layer without lead, cadmium of pigment without lead on ceramic glaze, and preparation method Download PDF

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Publication number
CN101050059B
CN101050059B CN200710015540A CN200710015540A CN101050059B CN 101050059 B CN101050059 B CN 101050059B CN 200710015540 A CN200710015540 A CN 200710015540A CN 200710015540 A CN200710015540 A CN 200710015540A CN 101050059 B CN101050059 B CN 101050059B
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lead
cadmium
pigment
ceramic glaze
cover layer
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CN101050059A (en
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徐博
钱鹏
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HUAWEI PIYMENTS CO Ltd ZIBO
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HUAWEI PIYMENTS CO Ltd ZIBO
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    • 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
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

This invention relates to a lead- and cadmium-free cover for lead-free overglaze pigment. The lead- and cadmium-free cover comprises: major components 80.0-95.0 wt.%, viscosity regulator 3.0-7 wt.%, stabilizer 1.0-7.0 wt.%, and coloring aid 1.0-8.0 wt.%. The major components are SiO2, Na2O and B2O3. The viscosity regulator is Al2O3. The stabilizer is one or more of ZrO2, SnO2 and La2O3. The coloring aid is one, two or three of MgO, CaO, ZnO, SrO and BaO. The lead- and cadmium-free cover can maintain the high performance of lead-free overglaze pigment, and can also reduce the stripping amount of lead and cadmium of the lead-free overglaze pigment, thus maintaining the original color of the lead-free overglaze pigment and preventing the pattern from cracking. The lead- and cadmium-free coveris colorless, and has such advantages as high adhesiveness, high adaptability and easy production.

Description

Covering layer without lead, cadmium of pigment without lead on ceramic glaze and preparation method thereof
Technical field
The present invention relates to a kind of covering layer without lead, cadmium of pigment without lead on ceramic glaze and preparation method thereof, belong to pottery, pigment technology field.
Background technology
The flux that is adopted in the ceramic industry all contains plumbous oxide basically, because plumbous oxide can make flux meltable and the melt temperature scope of broad arranged, can improve the refractive index and the elasticity of glass, can make the more rich reality of color of pigment, can also slow down alkalimetal ion dissociating in glass, have and the matched thermal expansivity of most of enamel, therefore, from ancient times to the present, on ceramic glaze, mostly adopt plumbous oxide in the lead-free pigment.But other metal oxides on plumbous compound and the ceramic glaze in the lead-free pigment and the compound of cadmium etc. all are deleterious, especially the tableware of decorating with over-glaze pigment, drinking utensils, tea set etc., in use, poisonous components such as lead, cadmium can weather and stripping, harm people's health, for addressing this problem, unremitting effort is being done always by the scientific research institution and the production department of ceramic industry both at home and abroad.
Chinese patent application numbers 911016120 discloses a kind of glass composition; its purpose provides a kind of unleaded surrogate; its formation is: silicon-dioxide 38～50%; zirconium white 9～17%; boron oxide 26～50%; sodium oxide or (with) potassium oxide 4～16%; 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% and fluorochemical 0～2%; the glass flux composition of forming; in order to constitute a kind of enamel composition; it is applied on the goods that burnt till, and twice firing plays the decoration provide protection.Its weak point is:
A, chemical stability are bad, low in glossiness.
B, to the paint color bad adaptability, can influence the colour generation of the color of fugitive colors such as golden red, iron oxide red, selenium ruby, cause aberration big, make the original picture distortion.
C, thermal expansivity are big, easily cause picture crackle or burst porcelain.
Summary of the invention
The object of the present invention is to provide a kind of covering layer without lead, cadmium of pigment without lead on ceramic glaze, the premium properties that can keep lead-free pigment on the ceramic glaze fully, colourless light, adhere firmly, can reduce the plumbous quantity of cadmium release of over-glaze pigment picture again greatly, keep original colour generation of paint color, adaptability is good, has prevented the picture cracking; The present invention provides simple and easy to do making method simultaneously.
Covering layer without lead, cadmium of pigment without lead on ceramic glaze of the present invention, its weight percent consists of:
SiO 2, Na 2O and B 2O 3The main body composition of forming 80.0～95.0%
Al 2O 3Viscosity modifier 3.0～7%
ZrO 2, SnO 2And La 2O 3In one or both or three kinds mix the stablizers of forming 1.0～7.0%
Among MgO, CaO, ZnO, SrO and the BaO one or both or three kinds of colour generation auxiliary agents 1.0～8.0% that mix composition.
Preferred weight percent compositing range is:
SiO 240～65%, B 2O 315～25%, Na 2O 5～10%, Al 2O 33～7%, K 2O 2～5%, ZrO 21～3%, SnO 21～3%, La 2O 30～1%, ZnO 1～5%, MgO 0～5%, CaO 0～5%, SrO 0～2% and BaO 0～2%.
Among the present invention:
Covering layer without lead, cadmium of pigment without lead on ceramic glaze, key problem in technology are to make it to have suitable thermal expansivity and to the high-fidelity performance of all colours colour generation.Na 2O-B 2O 3-SiO 2The sodium of system, boron, silex glass, its feature be thermal expansivity little, have higher thermostability, chemical stability and optical property, can meet design requirement well.
Viscosity modifier is the indispensable integral part of the present invention, and is because suitable cover layer viscosity can guarantee that picture pigment is colour-fast in roasting burning process, especially particularly evident for picture effects such as the iron oxide red of fugitive color, selenium ruby, golden red.
The ZrO of macromolecule in the stabilizer component 2, SnO 2Tightr Deng the network structure that makes glass, for the chemical stability that improves the cover layer has been made outstanding contribution, and the coefficient of expansion of their negative values has remedied the increase because of the caused coefficient of expansion of adding of basic metal and alkaline-earth metal fusing assistant.
Among MgO, the CaO that lead-free and cadmium-free cover layer is introduced, ZnO, SrO, the BaO, the colour generation auxiliary agent that chooses helps the colour generation of unleaded color in sintering process, particularly the pigment of fugitive colors such as golden red, iron oxide red, selenium ruby is played the effect of high-fidelity.
The making method of covering layer without lead, cadmium of pigment without lead on ceramic glaze of the present invention, simple and easy to do, at first found cover layer powder, and then execute on the product, carry out according to the following step successively:
(1), after fusion, shrend, is ground into a cover layer powder according to the proportion of composing of component preparation cover layer batching and mix;
(2) will cover layer powder is printed onto on the marble paper of pattern out of the press;
(3) marble paper that will be printed on cover layer is attached to the ceramic last time that desire decorates and burns till, and just forms the cover layer on the pattern.
Raw materials used technical pure chemical industry raw material or the reagent purifying worker raw material of being of component among the present invention, market is on sale, can directly buy.
Wherein: preferred control process parameters is respectively:
Melt temperature is 1300～1350 ℃.
Smashing fineness is controlled to be weight content 〉=90% of the particulate material of particle diameter≤5 μ m.
To cover layer powder and be printed onto on the marble paper with the stand linseed oil allotment, the weight proportion of cover layer powder and stand linseed oil is: 1: 0.8～1.0.
Firing temperature (also claiming the roasting temperature of burning) is: 700～800 ℃, and soaking time 8～20 minutes.
With covering layer without lead, cadmium of pigment without lead on ceramic glaze of the present invention and making method, can decorate the various ceramics of protection over-glaze pigment, be particularly useful for the ceramic of cooker, tableware, kitchenware.Goods picture lead release behind the Decorative Cover layer is 0.00mg/dm 2, quantity of cadmium release is less than 0.07mg/dm 2, and make original picture more moist.Concrete advantage of the present invention is as follows:
(1) thoroughly eradicates plumbous murder by poisoning, greatly reduced the unleaded stripping quantity that contains the cadmium dye cadmium.
(2) the roasting temperature of burning is low, energy-saving and cost-reducing.
(3) the colourless light of cover layer, adhere firmly to the lead-free pigment color adaption is good, transparency is high, aberration is little, thereby makes well colour generation of various pigment, comprises iron oxide red, selenium ruby and the golden red of fugitive color, does not make the original picture distortion.
(4) thermal expansivity is lower, and 4.5～6.8 * 10 -6C -1, adaptability is good, can not cause picture crackle or burst porcelain.
(5) making method is simple and easy to do, grasps easily, controls, and once-firing has been simplified technology, has avoided the wearing and tearing of picture on the glaze, has guaranteed quality product.
Embodiment
The invention will be further described below in conjunction with embodiment.
Covering layer without lead, cadmium of pigment without lead on ceramic glaze embodiment 1-8 of the present invention ingredients by weight percentage composition and main manufacture craft parameter see Table 1.
With the same color of lead-free pigment decoration on the ceramic glaze and the model of same picture, respectively behind the lead-free and cadmium-free cover layer processing decoration made from the embodiment 1～embodiment 8 shown in the table 1 with do not add lead-free and cadmium-free cover layer model, record lead, quantity of cadmium release mg/dm according to the method for ZBY24006～89 2Control case sees Table 2.
The same color of lead-free and cadmium-free cover layer processing decoration of decorating and making with the embodiment 1～embodiment 8 shown in the table 1 with lead-free pigment on the ceramic glaze and the model of picture equally, the aberration control case that records with the color colour-difference meter sees Table 3, and aberration Δ E value is all within the aberration scope of industry requirement.
(continued on next page)
Table 1, embodiment 1-8 ingredients by weight percentage composition and main manufacture craft parameter list
Embodiment 1 2 3 4 5 6 7 8
SiO 2 48.5 46.3 51.2 50.9 45.3 55.8 57.0 47.6
B 2O 3 19.2 21.5 23.6 24.2 18.1 22.5 20.9 20.0
Na 2O 5.5 6.3 8.8 7.9 5.8 9.0 9.8 5.3
Al 2O 3 6.7 6.3 4.1 5.5 5.9 3.2 3.5 6.4
K 2O 2.5 3.6 4.5 4.1 3.1 4.6 4.8 2.7
ZrO 2 2.5 2.5 1.2 1.3 2.2 1.2 1.4 2.3
SnO 2 2.8 2.6 1.5 1.5 2.9 1.5 1.3 2.0
La 2O 3 0.5 0.8 0.0 0.3 1.0 0.0 0.0 0.6
ZnO 4.0 4.5 4.1 1.5 4.2 1.6 1.3 3.9
MgO 1.1 2.0 0.0 0.0 3.1 0.6 0.0 2.8
CaO 3.2 0.0 0.0 1.0 4.5 0.0 0.0 2.5
SrO 1.5 1.8 1.0 0.8 2.0 0.0 0.0 1.9
BaO 2.0 1.8 0.0 1.0 1.9 0.0 0.0 2.0
Melt temperature (℃) 1300 1320 1350 1310 1330 1340 1350 1320
Embodiment 1 2 3 4 5 6 7 8
Ball milling fineness: the weight content % of the particulate material of particle diameter≤5 μ m 91 95 93 98 90 96 92 95
The weight ratio of cover layer powder and stand linseed oil 1∶0.8 1∶1 1∶1 1∶0.9 1∶1 1∶0.8 1∶1 1∶1
Roasting burning temperature (℃) 700 750 730 780 800 760 740 770
Soaking time minute 10 12 15 10 11 9 12 10
(continued on next page)
Table 2, lead, quantity of cadmium release (mg/dm 2) synopsis
Figure G2007100155407D00051
Table 3, aberration (Δ E) control case see Table 3
Iron oxide red Golden red Ochre Cadmium yellow Selenium ruby Cadmium is green
1 2.50 2.25 1.83 0.09 1.15 0.12
2 2.35 2.18 2.10 0.08 1.23 0.32
3 1.85 2.11 2.01 0.57 1.68 0.45
4 1.96 1.90 1.90 0.08 1.85 0.18
5 2.15 2.56 1.56 0.18 1.50 0.19
Iron oxide red Golden red Ochre Cadmium yellow Selenium ruby Cadmium is green
6 2.89 1.39 2.23 0.22 2.20 0.41
7 2.63 2.68 1.92 0.16 1.78 0.39
8 2.45 2.90 1.78 0.25 1.69 0.02

Claims (7)

1. covering layer without lead, cadmium of pigment without lead on ceramic glaze is characterized in that weight percent consists of:
SiO 251.2%, B 2O 323.6%, Na 2O 8.8%, Al 2O 34.1%, K 2O 4.5%, ZrO 21.2%, SnO 21.5%, ZnO 4.1% and SrO 1.0%.
2. the making method of the described covering layer without lead, cadmium of pigment without lead on ceramic glaze of claim 1 is characterized in that at first founding cover layer powder, and then executes on the product, carries out according to the following step successively:
(1), after fusion, shrend, is ground into a cover layer powder according to the proportion of composing of component preparation cover layer batching and mix;
(2) will cover layer powder is printed onto on the marble paper of pattern out of the press;
(3) marble paper that will be printed on cover layer is attached to the ceramic last time that desire decorates and burns till, and just forms the cover layer on the pattern.
3. the making method of covering layer without lead, cadmium of pigment without lead on ceramic glaze according to claim 2 is characterized in that melt temperature is 1350 ℃.
4. according to the making method of claim 2 or 3 described covering layer without lead, cadmium of pigment without lead on ceramic glaze, it is characterized in that the weight content that smashing fineness is controlled to be the particulate material of particle diameter≤5 μ m is 93%.
5. the making method of covering layer without lead, cadmium of pigment without lead on ceramic glaze according to claim 4 is characterized in that cover layer powder is printed onto on the marble paper with the stand linseed oil allotment.
6. the making method of covering layer without lead, cadmium of pigment without lead on ceramic glaze according to claim 5 is characterized in that the weight proportion that covers layer powder and stand linseed oil is: 1: 1.
7. the making method of covering layer without lead, cadmium of pigment without lead on ceramic glaze according to claim 6 is characterized in that firing temperature is: 730 ℃, and soaking time 15 minutes.
CN200710015540A 2007-05-15 2007-05-15 Covering layer without lead, cadmium of pigment without lead on ceramic glaze, and preparation method Expired - Fee Related CN101050059B (en)

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CN102850041A (en) * 2012-09-27 2013-01-02 厦门宏金丰贸易有限公司 Wine bottle manufacturing method
CN104231728B (en) * 2013-06-20 2016-07-06 佛山市高明绿色德化工有限公司 A kind of ultrawhite environmental protection safety glass ink and preparation method thereof
CN104974592A (en) * 2014-04-14 2015-10-14 佛山市高明绿色德化工有限公司 Multifunctional tempered glass oil ink and preparation method thereof
CN105256735A (en) * 2015-08-25 2016-01-20 崔文生 Glass reflection spike and preparation method thereof
CN105753513B (en) * 2016-01-23 2018-04-20 景德镇陶瓷大学 A kind of trailing of highly corrosion resistant ceramic glazing dyestuff
CN107201060B (en) * 2017-05-19 2019-05-17 淄博华为颜料有限公司 Lead-free low-temperature low cobalt ceramic glaze blueing pigment and its preparation method and application
CN109748514A (en) * 2019-03-08 2019-05-14 淄博宝晶新材料股份有限公司 A kind of environmental protection impact resistance glass pigment

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1042698A (en) * 1989-10-25 1990-06-06 山东省硅酸盐研究设计院 Low-temp ceramics over-glaze pigment and preparation method thereof
CN1128246A (en) * 1994-11-17 1996-08-07 山东省硅酸盐研究设计院 Leadless cadmiumless ceramic glazing pigment
CN1810693A (en) * 2005-01-24 2006-08-02 肖特股份公司 Lead-free and cadmium-free glass for glazing, enameling and decoration of glasses or glass-ceramics

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1042698A (en) * 1989-10-25 1990-06-06 山东省硅酸盐研究设计院 Low-temp ceramics over-glaze pigment and preparation method thereof
CN1128246A (en) * 1994-11-17 1996-08-07 山东省硅酸盐研究设计院 Leadless cadmiumless ceramic glazing pigment
CN1810693A (en) * 2005-01-24 2006-08-02 肖特股份公司 Lead-free and cadmium-free glass for glazing, enameling and decoration of glasses or glass-ceramics

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JP特开平11-43386A 1999.02.16

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