CN102643023B - Environmental-friendly black glaze for automotive glass and preparation method of black glaze - Google Patents
Environmental-friendly black glaze for automotive glass and preparation method of black glaze Download PDFInfo
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- CN102643023B CN102643023B CN201210137341.4A CN201210137341A CN102643023B CN 102643023 B CN102643023 B CN 102643023B CN 201210137341 A CN201210137341 A CN 201210137341A CN 102643023 B CN102643023 B CN 102643023B
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- China
- Prior art keywords
- black
- glass
- black glaze
- glaze
- automotive glass
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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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron 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
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
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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
The invention relates to a high-performance environmental-friendly black glaze for automotive glass and a preparation method of the black glaze. The invention is characterized in that the high-performance environmental-friendly black glaze for the automotive glass comprises the following compositions in percentage by weight: 75-80% of bismuth series low-melting- point glass powder and 20-25% of inorganic black pigment. The bismuth series glass powder contains ZnO without rare-earth oxides; the grain size of the glass powder is 0.5-3 um; and the inorganic black pigment is iron-chromium-nickel-manganese black pigment or chromium-copper black pigment. The glass powder and the inorganic pigment are added to a V-shaped blender mixer to be mixed in proportion, so that the black glaze for the automotive glass is obtained. And then the black glaze is blended into slurry by organic carrier, and is coated at the edge of the automotive glass through screen printing. a black framework of the automotive glass is formed through the processes such as low-temperature drying, hard fire and the like. The blackness value L is less than 7, and the shielding property Delta L is less than 1.
Description
Technical field
The present invention relates to a kind of high-performance environment protection type black glaze and preparation method thereof for vehicle glass.
Background technology
Vehicle glass is printed on the forward and backward windshield glass of automobile edge with black glaze.Burn till rear formation vehicle glass black surround, for attractive, decorative and anti-visible ray, ultraviolet light.Exempt to make tackiness agent aging and reduce cohesive force.High-performing car glass should meet auto-maker to the higher physics of black glaze and chemical property requirement with black glaze, for example (,) color, opacity, scratch resistance, resistance to wear, cohesive strength, chemical stability etc.
Color is the important appearance attribute of black glaze, has now developed into global demand.The color of black glaze requires more black (black level value L<7.5) better.Tone requires partially blue look.Namely black glaze is to visible ray (380-700 nanometer) for the opacity of black glaze, and the screening performance of UV-light (300-400 nanometer) is very important.Prevent that solar energy from seeing through, reduce the impact on glass glue sticking power.
Vehicle glass producer requires to use unleaded black glaze, and this is the measure of implementing according to environmental requirement.Industrial pollution causes acid rain meeting corrosive black glaze, for this reason, has formulated global higher acidproof standard.
High-performing car glass glass also should meet vehicle glass manufacturing technique requirent with black glaze, for example anti-adhesion performance when the firing temperature of black glaze, firing time, crystallization property, glass press shaping die.
The shaping processing of vehicle glass adopts the disposable press molding of mold.For preventing that mold from leaving a trace heat is on glass, contact surface will be added a cover pressing mold cloth.In pressurized operation, black glaze directly contacts with pressing mold cloth.So the anti-adhesion performance of black glaze is produced most important to being shaped in glass press shaping die process.If adhere, can cause black glaze defect, glass deformation, the overwear vt. of pressing mold cloth, even whole production line stops production.Improving constantly the requirement of black glaze anti-adhesion performance of vehicle glass production capacity is also higher.Vehicle glass is ℃ forming temperature from room temperature to 600-700, produces and is less than 3 minutes heat-up time.So the heat transfer performance of the firing temperature of black glaze, high-temperature fusion performance, crystallization property and black glaze is also very important with black glaze to high-performing car glass.
Rear window windshield glass with black glaze it be double exposure on defrost conductive silver paste heater wire and bus, the infiltration of burning till rear conductive layer silver can make black glaze dyeing.It is a salient features that determines black glaze quality that black glaze stops the ability of silver-colored penetration dyeing.
In patent US 6,624,104, announced a kind of B
2o
3content is low, does not contain the vehicle glass crown glass glaze of ZnO.Its glass ingredient is: Bi
2o
350-65%, SiO
228-38%, B
2o
30-2.8%, Al
2o
30-3%, TiO
20-4%, Na
2o 0-8%, K
2o 0-5%, Li
2o 0-4%.Glass powder and inorganic melanochrome are mixed in proportion.Black glaze has good solidity to corrosion.
Patent WO 00/41977 has announced a kind of vehicle glass glass glaze.Its glass ingredient is Nb
2o
50.1-15%, alkalimetal oxide <3%, ZnO<3%, B
2o
3<1%.Coloring oxide (CeO
2, Co
3o
4, Cr
2o
3, CuO, Fe
2o
3, MnO
2, MoO
3, NiO and V
2o
5) be 0.1-25%.Glass is by a kind of and multiple containing Bi
2o
3, SiO
2form with the glass of coloring oxide.Black glaze presents good chemical stability and anti-adhesion performance.
Patent US 2006/0172876A1 has announced a kind of vehicle glass glass glaze.For improving chemical durability of glass, in glass ingredient, added tantalum oxide.Its glass ingredient is SiO
28-45%, ZnO is not more than 7%, B
2o
3be not more than 4%, Bi
2o
3, 40-80%, Na
2o is not more than 4%, K
2o is not more than 8%, Li
2o is not more than 4%, Ta
2o
50.1-22%, Nb
2o
5be not more than 1%, Al
2o
3and TiO
2, ZrO
2and BaO is not more than 4%, SrO and Sb
2o
3, MgO, P
2o
5, Mo
2o
3and CaO is not more than 1%, F
2be not more than 3%La
2o
3and Pr
2o
3, Nd
2o
3and Ce
2o
3one or more be not more than 4%.
In the glass glaze component of announcing at patent WO 00/41977 and patent US 2006/0172876A1, all contain rare earth oxide so glass cost is high.Black glaze involved in the present invention is intended not containing rare earth oxide.
US 6,624, oxygen-freeization zinc in the 104 glass-glazed components of announcing.Different from it, in black glaze component involved in the present invention, contain zinc oxide.Work as especially Bi in glass ingredient
2o
3when content is low, the adding of the ZnO of high-content will be conducive to glass and be melt into.
Above two features, are built into main design of the present invention, when reducing costs and be conducive to glass and be melt into.
Summary of the invention
The object of the present invention is to provide a kind of high-performance environment protection type black glaze and preparation method thereof for vehicle glass.
High-performance environment protection type vehicle glass of the present invention by its component of black glaze and mass percent is: bismuth system glass powder with low melting point 75-80%, inorganic black pigment 20-25%.Described glass powder is Bi
2o
3-SiO
2-ZnO-B
2o
3system.The component of this system glass and mass percent are Bi
2o
313-65%, SiO
220-40%, ZnO 0.5-32%, B
2o
34-9%, Al
2o
30-3%, TiO
22-6%, Na
2o 0-5%, K
2o 0-5%, Sb
2o
30-4%, V
2o
50-5%.Described inorganic black pigment is commercially available siderochrome nickel manganese black pigment and chromium-copper black pigment.
Described high-performance environment protection type vehicle glass is as follows by the preparation method of black glaze:
(1) preparation of glass
Prepare glass raw materials by weight used and weigh, after mixing, be put in high temperature Muffle furnace and carry out glass melting.Temperature is controlled at 1300-1400 ℃, soaking time 50-70 minute.Glass melt after fusing is rolled into thin slice with two roller mills.Sheet glass makes the glass powder of required particle diameter through ball milling or comminution by gas stream.Glass powder particles scope is 0.5-3 μ m.
Described raw material is bismuth oxide, quartz sand, zinc oxide, boric acid, aluminum oxide, titanium dioxide, sodium carbonate or SODIUMNITRATE, salt of wormwood or saltpetre, Quilonum Retard, antimonous oxide and Vanadium Pentoxide in FLAKES.
(2) commercially available siderochrome nickel manganese black pigment or chromium-copper black pigment have good coloring effect to bismuth system glass.Step (1) is prepared to glass powder 75-80%(mass percent, lower same), inorganic black pigment 20-25%, adds V-type mixer batch mixing 1 hour, obtains the black glaze of uniform vehicle glass.
High-performance environment protection type vehicle glass of the present invention is the black glaze of a kind of crystal type glass with black glaze.And containing ZnO; Not containing rare earth oxide; By the control to black glaze crystal property, obtained the high-performing car glass black glaze that blackness, opacity, anti-adhesion performance meet the requirements and have good prevention silver penetration dyeing ability.Described black glaze is for front windshield or rear seat windscreen, and concrete grammar is that this black glaze of preparation is deployed into slurry with organic carrier, by silk screen printing, is coated in vehicle glass edge.Through oven drying at low temperature, high temperature the technique such as burns till and forms vehicle glass dark border.
Embodiment
High-performance environment protection type vehicle glass of the present invention is summarized in table 1 with each embodiment of black glaze
Table 1: the concrete composition of each embodiment
The black glaze of above-described embodiment can mix and use separately or by a certain percentage.
Above-described embodiment 1 is with embodiment 2 for front windshield, and embodiment 3 and embodiment 4 are for rear seat windscreen.The black glaze that each embodiment described above produces burns till rear satisfied:
(1) thermal expansivity is (85-95) * 10
-7/ ℃;
(2) acid resistance meets the requirements: soak 80 ℃ of 0.1NH
2sO
4be more than or equal to black glaze nondiscoloration in 40 hours;
(3) blackness value L<7;
(4) covering property △ L<1;
(5) the black glaze anti-adhesion performance of rear seat windscreen meets the requirements.
Claims (2)
1. the black glaze of eco-friendly car glass, is characterized in that black glaze for front windshield forms glass powder and consists of:
In described black glaze, bismuth glass powder mass percent is 77%, and the inorganic black pigment of chromium-copper is 23%.
2. the black glaze of eco-friendly car glass, is characterized in that black glaze for rear seat windscreen forms the percentage composition of bismuth glass opaque amount and is:
In described black glaze, bismuth glass powder mass percent is 76%, and black pigment mass percent is 24%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210137341.4A CN102643023B (en) | 2012-05-04 | 2012-05-04 | Environmental-friendly black glaze for automotive glass and preparation method of black glaze |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210137341.4A CN102643023B (en) | 2012-05-04 | 2012-05-04 | Environmental-friendly black glaze for automotive glass and preparation method of black glaze |
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| Publication Number | Publication Date |
|---|---|
| CN102643023A CN102643023A (en) | 2012-08-22 |
| CN102643023B true CN102643023B (en) | 2014-10-08 |
Family
ID=46656145
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210137341.4A Active CN102643023B (en) | 2012-05-04 | 2012-05-04 | Environmental-friendly black glaze for automotive glass and preparation method of black glaze |
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| CN (1) | CN102643023B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZW13689A1 (en) * | 1988-11-19 | 1989-12-12 | Johnson Matthey Plc | Glass composition for use in glazes or enamels |
| CN101544470A (en) * | 2009-04-20 | 2009-09-30 | 贵阳晶华电子材料有限公司 | High-bismuth-oxide dielectric material for electrode coating |
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2012
- 2012-05-04 CN CN201210137341.4A patent/CN102643023B/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563327A (en) * | 2019-10-17 | 2019-12-13 | 山东省淄博市博山长虹陶瓷装饰材料厂 | Special melanin for automobile glass and preparation method thereof |
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|---|---|
| CN102643023A (en) | 2012-08-22 |
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Effective date of registration: 20170327 Address after: 336000 Jiangxi city in Yichun Province Economic Development Zone No. 6 with spring Patentee after: Jiangxi Sunflex Light Retroreflective Material Co., Ltd. Address before: 318013 Taizhou, Zhejiang, East Taihe Road, No. 98, Jiaojiang Patentee before: Taizhou Directional Reflecting Materials Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 336000 Jiangxi city in Yichun Province Economic Development Zone No. 6 with spring Patentee after: Jiangxi shengfulai Optical Technology Co., Ltd Address before: 336000 Jiangxi city in Yichun Province Economic Development Zone No. 6 with spring Patentee before: JIANGXI SUNFLEX LIGHT RETROREFLECTIVE MATERIAL Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |