CN101255014A - Leadless cadmium-free reinforced glass pigment flux - Google Patents
Leadless cadmium-free reinforced glass pigment flux Download PDFInfo
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- CN101255014A CN101255014A CNA2008100148959A CN200810014895A CN101255014A CN 101255014 A CN101255014 A CN 101255014A CN A2008100148959 A CNA2008100148959 A CN A2008100148959A CN 200810014895 A CN200810014895 A CN 200810014895A CN 101255014 A CN101255014 A CN 101255014A
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- flux
- pigment
- glass
- cadmium
- reinforced glass
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Abstract
The invention relates to a lead and cadmium free toughened glass pigment flux, which can be prepared into glass pigment for decorating toughened glass. The composition of the burden by weight proportion is: 15-40% of SiO2, 5-30% of B2O3, 1-5% of Al2O3, 1-10% of TiO2, 5-20% of ZnO, 1-5% of ZrO2, 1-5% of SnO2, 1-15% of Li2CO3, 1-5% of K2O, 1-5% of Na2O, 1-5% of CaCO3and 0-5% of Ba2CO3. The pigment flux has the advantages of no lead, no cadmium, non-toxicity, safety, reliability, good chemical stability, pure color generation, gorgeous color, high glossiness and high quality, which is suitable for red, blue, green and yellow agent and can be manufactured into glass pigment for decorating toughened glass or other glassware. Since the cost is low, the pigment flux is beneficial for large-scale popularization.
Description
Technical field
The present invention relates to a kind of leadless cadmium-free reinforced glass pigment flux, be made into glass pigment and be used for tempered-glass decorative.
Background technology
Reinforced glass pigment is the pigment that (680～720 ℃ of tempering temperature) is printed on glass surface in the tempering process of glass.Reinforced glass pigment and glass fusing point are approximate, are melted on glassly, and its color is based on black, white, other red in addition, blue, green, yellow isochrome.Toughened glass is applied to vehicle glass, building glass, refrigerator internal partition, microwave oven glass screen and toughened glass ware etc. more.
With the sheet glass that fluorine method explained hereafter is come out, intensity is low, and is easily broken, and when particularly being applied in automobile and building field, the probability that people and glass bump against is bigger, and broken glass makes the people come to harm easily.Glass is through behind the tempering, and intensity will increase considerably, and when meeting accident collision, particulate state can appear in glass to be pulverized, and avoids causing personal injury, and therefore, toughened glass has obtained using widely.When glass carries out tempering, can or spray on glassly with the color-printed of identical fusing point, glass is carried out color and pattern decorative, therefore, need the research reinforced glass pigment.
The same with beramic color, reinforced glass pigment also is made up of flux and toner, and the main raw material in the flux is plumbous.This lacks the lead ore resource relatively in China, and lead is listed in strategic resource in China, is one of rare metal, and application is restricted.On the other hand, lead is being dug up mine, smelting and is being employed in the process, and plumbous obnoxious flavour is drained in the atmosphere, and environment is polluted, and HUMAN HEALTH is worked the mischief.And the main raw material plumbous oxide in the existing reinforced glass pigment flux has accounted for the 30-55% of gross weight, and its harm well imagines that the same with the development leadless cadmium-free ceramic pigment flux, the lead-free and cadmium-free flux for pigment that the suitable toughened glass of research is used is imperative.
Summary of the invention
The object of the present invention is to provide a kind of leadless cadmium-free reinforced glass pigment flux, the lead-free and cadmium-free nontoxicity, safe and reliable, chemical stability is good again, is fit to red, blue, green, yellow agent, and colour generation is pure, and is lucuriant in design, the glossiness height, quality is good.
Leadless cadmium-free reinforced glass pigment flux of the present invention, its ingredients by weight percentage composition is: SiO
215～40%, B
2O
35～30%, Al
2O
31～5%, TiO
21～10%, ZnO 5～20%, ZrO
21～5%, SnO
21～5%, Li
2CO
31～15%, K
2O 1～5%, Na
2O 1～5%, CaCO
31～5% and Ba
2CO
30～5%.
Best group becomes: SiO
220～35%, B
2O
38～25%, Al
2O
31～5%, TiO
21～10%, ZnO 5～15%, ZrO
21～5%, SnO
21～5%, Li
2CO
31～12%, K
2O 1～5%, Na
2O 1～5%, CaCO
31～5% and Ba
2CO
30～5%.
Identical with common flux preparation method, the desired raw material of buying is mixed in proportion, get final product through 1200～1300 ℃ of temperature fusions, shrend, oven dry.
Flux lead-free and cadmium-free nontoxicity of the present invention, safe and reliable, except that need not the oxide compound of plumbous cadmium, the influence stability that also need not existing domestic and international correlation technique adopted and the expensive Bi of color development
2O
3, only utilize the SiO of the cheapness of some routines
2, Al
2O
3And B
2O
3, the network constituting body of formation even compact, this lays a good foundation to preparation colour generation beramic color pure, that chemical stability is good.Composite fluxing agent by basic metal, alkaline-earth metal are formed when reducing the flux melt temperature, has improved the acid resistance of pigment greatly by mixed alkali effect.The acidic oxide ZrO of macromolecule low bulk
2, TiO
2And SnO
2Make the structure of flux tightr Deng not only, and cut down the increase of the caused coefficient of expansion of adding of basic metal and alkaline-earth metal, improved chemical stability.
Toner that uses among the present invention and the traditional toner that contains lead pigments are basic identical, no longer repeat.
The preparation method of leadless cadmium-free reinforced glass pigment flux of the present invention and the pigment directly technology of following conventional lines gets final product, and carries out according to the following step successively:
1. the preparation of flux: the solvent desired raw material of buying is mixed in proportion, through 1200～1300 ℃ of temperature fusions, shrend, dry for standby;
2. ball milling: flux and toner mixing and ball milling to grain diameter＜80 micron, are gone out to grind dry for standby; The weight proportion composition of flux and toner is generally: flux 60～85%, toner 15～40%;
3. select resintering or resintering not: resintering promptly: compound resintering (to increase the density and the vividness of pigment), shrend, oven dry under 700～800 ℃ temperature that ball milling is crossed;
4. regrind: the shrend material behind the resintering is reinstalled in the ball mill wet-milling to grain diameter＜5 micron, the pigment product of go out mill, oven dry, pulverizing.
Leadless cadmium-free reinforced glass pigment using method of the present invention is identical with common product, along with 680～720 ℃ the tempering decoration of finishing dealing with.
After testing, the product physical and chemical index of acquisition is as follows:
1. thermal expansivity: 80-95 * 10
-7℃
-1) utilize the 402E type electronic dilatometer of West Germany's product to record;
2. chemical stability: plumbous quantity of cadmium release is 0.00-0.1mg/dm
2, under 22 ± 2 ℃, soak under 24 hours or 60 ± 2 ℃ 0.5%Na in 4% acetum
2CO
3Soak after 40 hours in the solution, tone, color and luster do not have considerable change.
Leadless cadmium-free reinforced glass pigment flux of the present invention, the lead-free and cadmium-free nontoxicity, safe and reliable, chemical stability is good, is fit to multiple toners such as red, blue, green, yellow, black, wide adaptability, colour generation is pure, and is lucuriant in design, the glossiness height, quality is good, is made into the decoration that glass pigment is used for tempered-glass decorative or glassware.Because of cost is low, be beneficial to large-scale promotion.
Embodiment
The invention will be further described below in conjunction with embodiment.
The preparation method of reinforced glass pigment among the embodiment is to prepare burden according to forming, and prepares flux earlier, refabrication pigment, and step is successively:
1. the preparation of flux: in proportion the solvent desired raw material is mixed, through 1260 ± 20 ℃ of temperature melt water quenchings, dry for standby;
2. ball milling: flux and black developing agent or the white agent ball milling of packing in proportion is milled to grain diameter＜80 micron, goes out to grind dry for standby;
3. resintering: compound resintering, shrend under 750 ± 20 ℃ temperature that ball milling is crossed;
4. regrind: the shrend material behind the resintering is reinstalled in the ball mill wet-milling to grain diameter＜5 micron, go out mill, oven dry, pigment gets product after pulverizing.
The composition of beramic color and flux sees Table 1 on the described glaze of wood inventive embodiments.
Beramic color and flux ingredients by weight percentage composition table on table 1, the embodiment 1-5 glaze
Each embodiment technical target of the product sees Table 2.
Table 2, embodiment 1-5 technical indicator table
| The barbecue temperature (℃) | Acid and alkali-resistance | Plumbous quantity of cadmium release (mg/dm 2) | The coefficient of expansion (* 10 -7℃ -1) | |
| Embodiment 1 | 750±20 | Soak the back and observe no change | 0 | 82 |
| Embodiment 2 | 750±20 | Soak the back and observe no change | 0 | 90 |
| Embodiment 3 | 750±20 | Soak the back and observe no change | 0 | 92 |
| Embodiment 4 | 750±20 | Soak the back and observe no change | 0 | 85 |
| Embodiment 5 | 750±20 | Soak the back and observe no change | 0 | 88 |
Claims (2)
1, a kind of leadless cadmium-free reinforced glass pigment flux is characterized in that its ingredients by weight percentage composition is: SiO
215～40%, B
2O
35～30%, Al
2O
31～5%, TiO
21～10%, ZnO 5～20%, ZrO
21～5%, SnO
21～5%, Li
2CO
31～15%, K
2O 1～5%, Na
2O 1～5%, CaCO
31～5% and Ba
2CO
30～5%.
2, leadless cadmium-free reinforced glass pigment flux according to claim 1 is characterized in that its ingredients by weight percentage composition is: SiO
220～35%, B
2O
38～25%, Al
2O
31～5%, TiO
21～10%, ZnO 5～15%, ZrO
21～5%, SnO
21～5%, Li
2CO
31～12%, K
2O 1～5%, Na
2O 1～5%, CaCO
31～5% and Ba
2CO
30～5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100148959A CN101255014A (en) | 2008-03-26 | 2008-03-26 | Leadless cadmium-free reinforced glass pigment flux |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100148959A CN101255014A (en) | 2008-03-26 | 2008-03-26 | Leadless cadmium-free reinforced glass pigment flux |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101255014A true CN101255014A (en) | 2008-09-03 |
Family
ID=39890179
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100148959A Pending CN101255014A (en) | 2008-03-26 | 2008-03-26 | Leadless cadmium-free reinforced glass pigment flux |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101255014A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111302647A (en) * | 2020-03-30 | 2020-06-19 | 山东省淄博市博山长虹陶瓷装饰材料厂 | Zinc and boron-free glass pigment flux and preparation method and application thereof |
-
2008
- 2008-03-26 CN CNA2008100148959A patent/CN101255014A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111302647A (en) * | 2020-03-30 | 2020-06-19 | 山东省淄博市博山长虹陶瓷装饰材料厂 | Zinc and boron-free glass pigment flux and preparation method and application thereof |
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|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080903 |