CN101707172B - Black sizing agent with low photosensitivity for PDP front substrate and preparation method thereof - Google Patents
Black sizing agent with low photosensitivity for PDP front substrate and preparation method thereof Download PDFInfo
- Publication number
- CN101707172B CN101707172B CN2009100353464A CN200910035346A CN101707172B CN 101707172 B CN101707172 B CN 101707172B CN 2009100353464 A CN2009100353464 A CN 2009100353464A CN 200910035346 A CN200910035346 A CN 200910035346A CN 101707172 B CN101707172 B CN 101707172B
- Authority
- CN
- China
- Prior art keywords
- black
- parts
- nitrine
- sizing agent
- materials
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Fee Related
Links
Abstract
The invention relates to black sizing agent with low photosensitivity for a PDP front substrate. The black sizing agent comprises the following components in part by mass: 1-5 parts of azide used as a photosensitive crosslinker, 5-20 parts of non-photosensitive polymer resin, 10-35 parts of glass powder with low melting point, 5-35 parts of black pigment, 10-40 parts of organic solvent, 0.1-1 part of nanometer silver powder, 0-1 part of coupling agent and 0-1 part of flatting agent, wherein the azide is used as a photosensitive crosslinker; and the black pigment is a composite which is prepared by the following methods of: ball-milling and mixing two or more than two of Co3O4, Fe2O3, Ni2O3 and MnO2 uniformly and proportionally; placing the materials into a high-aluminum crucible to sinterfor 2 to 4 hours at the temperature of between 1,200+/-50 DEG C; pouring the materials quickly into cold water to quench; ball-milling the materials by a planetary ball mill; adding a certain amount of Bi2O3 into the materials to mix uniformly after the materials are dried; then performing secondary sintering on the mixture for 1 to 3 hours at the temperature of between 1,200+/-50 DEG C; and ball-milling the mixture to 0.8 to 3 microns.
Description
Technical field
The present invention relates to a kind of unleaded black sizing agent with low photosensitivity, be mainly used in the black layer of bus electrode structure on Plasmia indicating panel (PDP) prebasal plate.
Background technology
The color plasma flat-panel monitor forms the target of selecting into people because of its large-screen, high imaging quality, high-resolution.One of difficulty that plasma scope will overcome will reduce exactly to conflux width of (Bus) electrode improves its positional precision.Utilize the photosensitive paste method can realize large tracts of land, high meticulous electrode pattern, and technology and equipment needed thereby are simple, be easy to realize that therefore, the meticulous Bus electrode that adopts the photosensitive paste legal system to make PDP just becomes one of approach of the preferential selection that improves the PDP performance in the PDP development process.
Bus electrode on the prebasal plate comprises white conductive layer and black layer.The white conductive layer plays the electrode effect, is made up of conducting metal with high conductivity and glass dust.Black layer is used to improve contrast, and it is made up of glass dust and black pigment.This technology realizes by silk screen print method at present.The black light sensitive slurry is coated on the whole surface of prebasal plate of PDP, utilizes infra-red drying to form black layer, exposure, development, sintering.Apply the photosensitive conducting slurry be used to form conductive layer then, the dry conductive layer that forms exposes, development, sintering once more.Obtain the two-layer electrode figure.Application number 200710132248.3 lead-free photosensitive black medium slurry for shadow mask type PDP and preparation method, described black paste is the high photosensitivity slurry.
At present, the slurry that forms black layer mainly is a high photosensitivity light sensitivity black paste, because black paste will experience twice oven dry in bus electrode manufacturing process, double exposure, twice development, twice sintering may cause the hot curing of black photosensitive layer like this, thereby is unfavorable for the making of bus electrode.Simultaneously, present widely used photosensitive black slurry bin stability is relatively poor, and solidify easily the long-time back of placing, and cost of manufacture is higher, and the blackness that forms black layer is not enough, and contrast is low.
Summary of the invention
The present invention seeks to: the black sizing agent with low photosensitivity that proposes a kind of PDP of being used for prebasal plate.Especially cost is low, excellent storage stability; The blackness of black layer is good, good contrast, and in the manufacturing process of plasma scope prebasal plate, the Heat stability is good of black paste, technological operation is simple.
Technical scheme of the present invention is as follows: a kind of black sizing agent with low photosensitivity that is used for the PDP prebasal plate, and its component and quality group become: the macromolecule resin of 5-20 part; 10-35 part glass powder with low melting point; The black pigment of 5-35 part; The triazo-compound of 1-5 part; The organic solvent of 10-40 part; 0.1-1 the nano-silver powder of part; The coupling agent of 0-1 part; The levelling agent of 0-1 part.
Black pigment is the compound for preparing as follows: with Co
3O
4, Fe
2O
3, Ni
2O
3, Cr
2O
3, MnO
2In ball milling is even in proportion more than two kinds or two kinds, again this material is put into the high alumina crucible, 1200 ± 50 ℃ of insulations are poured material in the cold water into rapidly after 2-4 hour and are quenched, and use the planetary ball mill ball milling, oven dry back adding Bi
2O
3, after mixing, black pigment and Bi
2O
3Mass ratio 10: 0.2-2 carries out double sintering 1-3h at 1200 ± 50 ℃ again, and ball milling is to 0.8-3 μ m, dry for standby.
The triazo-compound of the black sizing agent with low photosensitivity of the described PDP of being used for prebasal plate is 4,4 '-two nitrine talan-2,2 '-sodium disulfonate; 4,4 '-two nitrine stilbenes-2,2 ' sodium disulfonate; 4,4 '-two nitrine stilbenes-2,2 ' sodium disulfonate; 4,4 '-two nitrine naphthalenes-3,7 ' sodium disulfonate; 2,5-two (4 '-azido-2 '-sulfo group benzal) cyclopentanone sodium disulfonate; 4,4 '-two nitrine Bians fork acetone; 4,4 '-two (4 '-nitrine benzal) cyclohexanone.
The described black sizing agent with low photosensitivity glass powder with low melting point that is used for the Plasmia indicating panel prebasal plate is Bi
2O
3-SiO
2-B
2O
3-BaO-ZnO-ZrO
2System lead-free glass powder, its softening point are 400 ℃, and particle diameter is 0.8-3.0 μ m.
With black pigment, glass powder with low melting point, nano-silver powder, triazo-compound, macromolecule resin, solvent by said ratio, after mixing with planetary mixer, carry out three-roll rolling get final product slurry; Wherein black pigment, glass powder with low melting point mix with the planetary ball mill ball milling earlier by above-mentioned part by weight.
The invention has the beneficial effects as follows: compared with prior art, the invention provides a kind of unleaded black paste that is used for the Plasmia indicating panel prebasal plate and preparation method thereof.The black paste of preparation, use triazo-compound and replace light sensitivity monomer and initator, have low photosensitivity, improved the thermal stability and the bin stability of slurry, technological operation is simple, with twice printing of bus electrode, twice drying, single exposure, once develop, once sintered, as to make combination electrode fineness height, contraposition is accurate; Simultaneously, the black pigment of the present invention preparation, the blackness height of the bus electrode of making has increased the contrast of display screen, has huge market application foreground.Cost of the present invention is low, excellent storage stability; The blackness of black layer is good, good contrast, and in the manufacturing process of plasma scope prebasal plate, the Heat stability is good of black paste, the present invention reaches good dispersiveness with black pigment powder and glass powder with low melting point ball milling together in addition, thereby has improved the blackness behind the black paste sintering.
Embodiment
The preparation of superfine low melting point lead-free glass powder: by set of dispense ratio ball milling in the agate jar, mix with chemical pure raw material.This material is put into the high alumina crucible, and 600 ℃ of chargings, are poured glass metal in the cold water into rapidly and are quenched after 2 hours in 1200 ℃ of insulations, with dry for standby behind the extremely certain particle diameter of planetary ball mill ball milling.
The preparation method of black pigment: with Co
3O
4, Fe
2O
3, Ni
2O
3, Cr
2O
3, MnO
2In ball milling is even in proportion more than two kinds or two kinds, again this material is put into the high alumina crucible, 1200 ℃ of insulations are poured material in the cold water into rapidly after 2-4 hour and are quenched, and use the planetary ball mill ball milling, a certain amount of Bi of oven dry back adding
2O
3, after mixing, carrying out double sintering 1-3h at 1200 ℃ again, ball milling is to certain particle diameter, and is standby.
The modulation of black paste: glass powder with low melting point and the black pigment by formula rate mixes earlier, and be behind planetary ball mill ball milling certain hour, standby.Mixture behind the ball milling, nano-silver powder, triazo-compound and additive are added in the carrier of being made by macromolecule resin and solvent in proportion, after mixing with planetary mixer, carry out three-roll rolling and get final product.Testing size fineness, viscosity.
Further explain the present invention below in conjunction with embodiment.
Described lead-free glass powder prescription consists of (wt part): Bi
2O
345 parts～80 parts, with two kinds to five kinds of following five kinds of media mixed: SiO
24～30 parts, B
2O
310～30 parts, 2～30 parts of ZnO, Al
2O
32～30 parts, 2～30 parts of BaO, black crown glass particle diameter is at 0.8～3 μ m;
Macromolecule resin is acrylic resin, poly-(MMA-CO-MAA), ethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose one or both.
Described other additives comprise the plasticizer phthalic acid dioctyl ester, butyl carbitol acetate, and epoxidized soybean oil or DOA etc., surfactant comprises lecithin, ethanol, cyclohexanone or the like.
Embodiment 1: form the preparation of the black sizing agent with low photosensitivity of bus electrode black layer
18 parts macromolecule resin (poly-(MMA-CO-MAA), molecular weight 15000g/mol), 30 parts black pigment (50 parts of Co-Fe-Mn-O and 50 parts of Bi
2O
3, average grain diameter=1.1 μ m), and 1 part nanometer Ag powder (average grain diameter=80nm), 15 parts glass dust (average grain diameter=1.5 μ m, D
Max=3.0 μ m, amorphous, Bi
2O
3-SiO
2-B
2O
3-BaO-ZnO-ZrO
2), 1 part triazo-compound (4,4 '-two nitrine talan-2,2 ' sodium disulfonate), 34 parts organic solvent (TMPD mono isobutyrate), 1 part of coupling agent (N-β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane), 1 part levelling agent (BYK-354) mixes to be incorporated in the blender and stirs, be equipped with black paste with three-roll rolling mechanism then, above ratio all by weight.Elder generation mixes the glass powder with low melting point and the black pigment of formula rate before the preparation black paste, with the planetary ball mill ball milling regular hour.
Embodiment 2: form the preparation of the black sizing agent with low photosensitivity of bus electrode black layer
12 parts macromolecule resin (poly-(MMA-CO-MAA), molecular weight 15000g/mol), 18 parts black pigment (80 parts of Co-Fe-Mn-O and 20 parts of Bi
2O
3, average grain diameter=1.1 μ m), and 1 part nanometer Ag powder (average grain diameter=80nm), 27 parts glass dust (average grain diameter=1.5 μ m, D
Max=3.0 μ m, amorphous, Bi
2O
3-SiO
2-B
2O
3-BaO-ZnO-ZrO
2), 5 parts triazo-compound (4,4 '-two nitrine stilbenes-2,2 ' sodium disulfonate, 4,4 '-two nitrine naphthalenes-3, the mixture of 7 ' sodium disulfonate and 2,5-two (4 '-azido-2 '-sulfo group benzal) cyclopentanone sodium disulfonate), 36 parts solvent (TMPD mono isobutyrate), 1 part of coupling agent (N-β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane), 1 part levelling agent (BYK-354) mixes to be incorporated in the blender and stirs, be equipped with black paste with three-roll rolling mechanism then, above ratio all by weight.Elder generation mixes the glass powder with low melting point and the black pigment of formula rate before the preparation black paste, with the planetary ball mill ball milling regular hour.
Embodiment 3: form the preparation of the black sizing agent with low photosensitivity of bus electrode black layer
16 parts macromolecule resin (poly-(MMA-CO-MAA), molecular weight 15000g/mol), 23 parts black pigment (65 parts of Co-Fe-Mn-O and 35 parts of Bi
2O
3, average grain diameter=1.1 μ m), and 1 part nanometer Ag powder (average grain diameter=80nm), 22 parts glass dust (average grain diameter=1.5 μ m, D
Max=3.0 μ m, amorphous, Bi
2O
3-SiO
2-B
2O
3-BaO-ZnO-ZrO
2), 3 parts triazo-compound (4,4 '-two nitrine talan-2,2 ' sodium disulfonate, 4, the mixture of 4 '-two nitrine Bians fork acetone and 4,4 '-two (4 '-nitrine benzal) cyclohexanone), 34 parts solvent (TMPD mono isobutyrate), 1 part of coupling agent (N-β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane), 1 part levelling agent (BYK-354) mixes to be incorporated in the blender and stirs, and is equipped with black paste with three-roll rolling mechanism then, and above ratio all by weight.Elder generation mixes the glass powder with low melting point and the black pigment of formula rate before the preparation black paste, with the planetary ball mill ball milling regular hour.
Embodiment 4: form the preparation of the photosensitive silver paste of low photosensitivity of bus electrode conductive layer
(sphere, the heap real density is 4.7g/cm to 65 parts Ag powder
3, average grain diameter=1.8 μ m), 5 parts inorganic bond (average grain diameter=1.5 μ m, D
Max=3.0 μ m, amorphous, Bi
2O
3SiO
2-B
2O
3-Al
2O
3-ZrO
2), 6 parts acrylic copolymer (poly-BMA Co-HEMA-CO-MAA, molecular weight 25000g/mol), 3 parts light trigger (1-is to morpholinyl phenyl-2-dimethylamino-2-benzyl-1-butanone), 8 parts photosensitive monomer (double pentaerythritol C5 methacrylate), 11 parts solvent (TMPD mono isobutyrate), 1 part of coupling agent (γ-glycidyl ether oxygen propyl trimethoxy silicane), 1 part levelling agent (BYK-354) mixes to be incorporated in the blender and stirs, be equipped with photosensitive silver paste with three-roll rolling mechanism then, above ratio all by weight.
Performance test:
Use-case 1,2, each black paste in 3 is used to form black layer, and the photosensitive silver paste in the use-case 4 is used to form conductive layer, makes layer bus electrodes.Resistance and blackness measurement to the bus electrode that utilizes the preparation of every kind of black paste are used for comparison.
1) utilize silk screen printing, with example 1,2, each black paste in 3 is printed in respectively on the plasma panel front glass substrate.
2) coating is in IR bake, and drying is 10 minutes under 100 ℃.
3) use screen printer print on the coating of every kind of drying the light sensitivity silver paste in the example 4.
4) double-decker of gained is in IR bake, and drying is 10 minutes under 100 ℃.
5) Gan Zao double-decker utilization has the uv-exposure equipment of high-pressure mercury lamp, is 500mJ/cm with exposure
2Ultraviolet photoetching.
6) structure of gained is at nozzle exit pressure 1.0kgf/cm
2, under 30 ℃, be 0.3 part sodium carbonate liquor spraying with concentration, develop.
7) structure of gained in sintering furnace, 580 ℃ of down insulations 15 minutes, obtain layer bus electrodes.
The evaluation result of the layer bus electrodes of making according to said process is shown in the following table.
| Characteristic | Example 1 | Example 2 | Example 3 |
| Black layer thickness behind the sintering (μ m) | 1.7 | 1.4 | 1.6 |
| Conductive layer thickness behind the sintering (μ m) | 4.2 | 3.8 | 4.1 |
| Linear resistance | 38.7 | 41.5 | 39.9 |
| Color | Black | Black | Black |
As can be seen from the above table, black paste provided by the present invention, the color of all electrodes is black, and combination property all can well satisfy the requirement of plasma display electrode.
The invention provides a kind of unleaded black paste of low photosensitivity that is used for the Plasmia indicating panel prebasal plate and preparation method thereof.Be characterized in the black paste that the present invention prepares, use triazo-compound and replace light sensitivity monomer and initator, have low photosensitivity, improved the thermal stability and the bin stability of slurry, technological operation is simple, with twice printing of bus electrode, twice drying, single exposure, once develop, once sintered, as to make combination electrode fineness height, contraposition is accurate; Simultaneously, the black pigment of the present invention preparation, the blackness height of the bus electrode of making has increased the contrast of display screen, has huge market application foreground.In addition black pigment powder and glass powder with low melting point ball milling are together reached good dispersiveness, thereby improved the blackness behind the black paste sintering.Technical indicator is from fineness, conductivity and can finish the level that all reaches batch process on the performance index of silver electrode.
Claims (2)
1. a black sizing agent with low photosensitivity that is used for the PDP prebasal plate is characterized in that, the quality component of black paste is: the triazo-compound of 1-5 part is as photosensitive crosslinker; The non-photosensitive macromolecule resin of 5-20 part; 10-35 part glass powder with low melting point; The black pigment of 5-35 part; The organic solvent of 10-40 part; 0.1-1 the nano-silver powder of part; The coupling agent of 0-1 part; The levelling agent of 0-1 part; Black pigment is the compound for preparing as follows: with Co
3O
4, Fe
2O
3, Ni
2O
3, Cr
2O
3, MnO
2In ball milling is even in proportion more than two kinds or two kinds, again this material is put into the high alumina crucible, 1200 ± 50 ℃ of insulations are poured material in the cold water into rapidly after 2-4 hour and are quenched, and use the planetary ball mill ball milling, oven dry back adding Bi
2O
3Mix black pigment and Bi
2O
3Mass ratio 10: 0.2-2 carries out double sintering 1-3h at 1200 ± 50 ℃ again, and ball milling is to 0.8-3 μ m; Described triazo-compound is 4,4 '-two nitrine talan-2,2 '-sodium disulfonate, 4,4 '-two nitrine stilbenes-2,2 ' sodium disulfonate, 4,4 '-two nitrine naphthalenes-3,7 ' sodium disulfonate, 2,5-two (4 '-azido-2 '-sulfo group benzal) cyclopentanone sodium disulfonate, 4,4 '-two nitrine Bians fork acetone or 4, one or more in 4 '-two (4 '-nitrine benzal) cyclohexanone.
2. the black sizing agent with low photosensitivity that is used for the PDP prebasal plate according to claim 1 is characterized in that, described glass powder with low melting point is Bi
2O
3-SiO
2-B
2O
3-BaO-ZnO-ZrO
2System lead-free glass powder, its softening point are about 400 ℃, and particle diameter is 0.8-3.0 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100353464A CN101707172B (en) | 2009-09-25 | 2009-09-25 | Black sizing agent with low photosensitivity for PDP front substrate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100353464A CN101707172B (en) | 2009-09-25 | 2009-09-25 | Black sizing agent with low photosensitivity for PDP front substrate and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101707172A CN101707172A (en) | 2010-05-12 |
| CN101707172B true CN101707172B (en) | 2011-11-09 |
Family
ID=42377387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100353464A Expired - Fee Related CN101707172B (en) | 2009-09-25 | 2009-09-25 | Black sizing agent with low photosensitivity for PDP front substrate and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101707172B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113667262A (en) * | 2021-08-27 | 2021-11-19 | 东莞市宇捷实业投资有限公司 | High-strength weather-resistant ABS composite material and preparation method thereof |
-
2009
- 2009-09-25 CN CN2009100353464A patent/CN101707172B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101707172A (en) | 2010-05-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101891390B (en) | Lead-free medium slurry and manufacturing method thereof | |
| CN101794639B (en) | Environment-friendly glass frit and preparation method thereof | |
| US7795165B2 (en) | Lead-free bismuth glass | |
| CN103097318B (en) | Zinc oxide-based glass frit composition and aluminum paste composition for back contact of solar cell using the same | |
| CN101697337B (en) | Low-silver photosensitive silver paste for PDP site selection electrodes, and preparation method thereof | |
| CN102044395A (en) | Method for directly preparing two-layer electrode by one-time silk-screen printing and used slurry thereof | |
| CN101728148B (en) | Electrode paste, electrode made from same, manufacturing methods thereof and PDP display screen provided with electrode | |
| CN106098144A (en) | A kind of glass dust and with its solar cell front side silver paste prepared and preparation method thereof | |
| EP1950766A2 (en) | A conductive composition ansd a rear substrate of a plasma display | |
| CN101685736A (en) | Transparent dielectric paste | |
| CN101177560B (en) | Lead-less photosensitive transparent medium slurry for shadow-mask type PDP and preparation method thereof | |
| CN101165837B (en) | Lead-free photosensitive black medium slurry for shadow mask type PDP and its preparation method | |
| CN101707172B (en) | Black sizing agent with low photosensitivity for PDP front substrate and preparation method thereof | |
| CN102426875B (en) | Conductive paste, preparation method thereof and electrode prepared from conductive paste | |
| CN102082056B (en) | Dielectric glass powder for plasma display panel | |
| CN101717196A (en) | Lead-free glass composition, preparation method and plasma display device using same | |
| CN101723597B (en) | Glass dust used for forming dielectric layer, size composition and display applying same and electrical appliance including the display | |
| US20110140054A1 (en) | Composition for preparing bus electrode and plasma display panel including electrode prepared therefrom | |
| EP1739688A1 (en) | Method for manufacturing a conductive composition and a rear substrate of a plasma display | |
| CN102479567A (en) | Electrode slurry composition and plasma display panel electrode made of the same | |
| JP2013151591A (en) | Inorganic particles-containing paste, and inorganic circuit | |
| CN101811830A (en) | Lead-free glass powder for dielectric layer | |
| CN101819380A (en) | Pulp for black optical imaging electrode of plasma display panel | |
| CN102426870B (en) | Electrode paste for plasma display panels, preparation method thereof and electrodes prepared from paste | |
| CN117125902A (en) | Sizing agent for automobile laminated glass and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20120813 Granted publication date: 20111109 |
|
| PD01 | Discharge of preservation of patent |
Date of cancellation: 20130213 Granted publication date: 20111109 |
|
| PP01 | Preservation of patent right |
Effective date of registration: 20130301 Granted publication date: 20111109 |
|
| RINS | Preservation of patent right or utility model and its discharge | ||
| PD01 | Discharge of preservation of patent |
Date of cancellation: 20130901 Granted publication date: 20111109 |
|
| PP01 | Preservation of patent right |
Effective date of registration: 20130901 Granted publication date: 20111109 |
|
| RINS | Preservation of patent right or utility model and its discharge | ||
| PD01 | Discharge of preservation of patent |
Date of cancellation: 20140301 Granted publication date: 20111109 |
|
| RINS | Preservation of patent right or utility model and its discharge | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20111109 Termination date: 20130925 |