# Patent

## Title
Black conductive thick film compositions, black electrodes, and methods of forming thereof

## Abstract

This invention is directed to black conductive compositions, black electrodes made from such compositions and methods of forming such electrodes.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit under 35 U.S.C. 119(e) of U.S Provisional Application Nos. 60/660,126 filed Mar. 9, 2005, 60/659,839 filed Mar. 9, 2005, 60/660,013 filed Mar. 9, 2005, 60/690,283 filed Jun. 14, 2005 and U.S. National patent application Ser. No. 11/369,549 filed Mar. 7, 2006, Ser. No. 11/369,550 filed Mar. 7, 2006, and Ser. No. 11/369,551 filed Mar. 7, 2006.


FIELD OF THE INVENTION
The present invention is directed to black conductive compositions, black electrodes made from such compositions and methods of forming such electrodes, more specifically the present invention is directed to the use of such compositions, electrodes, and methods in flat panel display applications, including alternating-current plasma display panel devices (AC PDP). The invention is further directed to AC PDP devices themselves.
BACKGROUND OF THE INVENTION
While the background of the present invention is discussed in terms of plasma display panel (PDP) applications, it is sunderstood that the present invention is useful in flat panel display applications, in general.
The PDP typically comprises a pair of forward and backward insulation substrates arranged in opposition to each other to form a plurality of cells as display elements each defined by the insulation substrates supported with a constant interval and cell barriers arranged between the insulation substrates, two crossing electrodes disposed on internal surfaces of the insulation substrates with a dielectric layer interposed between the electrodes which cause electric discharge in a plurality of cells by application of an alternating current. Due to this application of alternating current, phosphor screens formed on the wall surface of the cell barrier emit light and display images which are passed through the transparent insulation substrate (typically called the front glass substrate or plate).
One area of concern for PDP manufacturers is display contrast, which affects the ultimate picture viewed by the consumer. To improve the display contrast, it is essential to decrease the reflection of external light from the electrodes and conductors arranged on the front glass substrate of the PDP device. This reflection decrease can be accomplished by making the electrodes and conductors black as viewed through the front plate of the display.
Furthermore, another area of concern for PDP manufacturers is environmental in nature and is the lead and cadmium contained in the prior art black conductor compositions and black electrodes of the PDP device. It is desirable to reduce and/or eliminate the lead and cadmium contained in the black conductor compositions and electrodes while still maintaining the required physical and electrical properties of the compositions and electrodes.
For example, in Japanese Kokai Patent No. HEI 10[1998]-73233 and its division Japanese Kokai Patent No. 2004-158456, light-forming black electrode compositions containing conductive particles consisting of at least one substance chosen from ruthenium oxide, ruthenium polyoxide, or their mixture and an inorganic binder, black electrodes using such compositions, plasma display panels using such black electrodes, and a method for making such a plasma display panel are disclosed. These literature references are not directed to lead-free black conductive compositions. In these references, there are no descriptions of lead-free black conductive compositions in terms of properties such as the appearance and strength of black electrodes obtained by sintering the compositions, electrical properties such as resistance, and a balance of all the properties for PDP electrodes.
Japanese Patent No. 3510761 discloses alkali-developable photocurable conductive paste compositions for plasma display panels, easily forming high-precision electrode circuits on large areas by photolithography and firing below 600° C. Such compositions contain (A) copolymer resins obtained by the addition of glycidyl acrylate and/or glycidyl methacrylate to copolymers of methyl methacrylate and methacrylic acid and/or acrylic acid; (B) photochemical polymerization initiator; (C) photopolymerizable monomer; (D) at least one conductive metal powder selected from Au, Ag, Ni, and Al; (E) glass frit; and (F) a phosphoric acid compound. In this literature, a low-melting glass frit is described using lead oxide as the preferred main component, while there are no descriptions of lead-free conductive compositions, especially black conductive compositions.
Japanese Patent No. 3541125 discloses alkali-developable curable conductive paste compositions that have adhesion to the substrate after being fired, with adhesion between layers, suppression of curling, easy formation of high-precision conductive circuit patterns in large areas by photolithography, and are especially useful for forming underlayer electrode circuits of bus electrodes formed on the front substrate of plasma display panel. These compositions consist of: (A) carboxy-group-containing resins; (B) photopolymerizable monomer; (C) photochemical polymerization initiator; (D) silanol-group-containing synthetic amorphous silica fine powder; (E) conductive powder; and if needed (F) heat-resistant black pigment; (G) glass frit; and (H) stabilizer. In particular, this literature has a description of a low-melting glass frit using lead oxide as the preferred main component, while there are no descriptions of lead-free conductive compositions, especially black conductive compositions.
Japanese Patent No. 3479463 discloses photocurable conductive compositions providing adhesion on a substrate in steps involving drying, exposure, development and firing, and resolution, satisfying the need for both a sufficient conductivity and blackness after being fired and discloses plasma display panels (PDP) with formation of the underlayer (black layer) electrode circuit using such compositions. The basic first embodiment of the compositions described in this literature contains (A) black conductive microparticles having a surface area to weight ratio larger than 20 m2/g and containing at least one substance chosen from ruthenium oxide or other ruthenium compound, copper-chromium black composite oxide and copper-iron black composite oxide, (B) an organic binder, (C) a photopolymerizable monomer, and (D) a photochemical polymerization initiator. The second embodiment contains (E) inorganic fine particles in addition to the above components. In this literature, with respect to this composition, the inorganic fine particles (E) contain, as needed, glass powder with a softening point of 400-600° C., conductive powder, heat-resistant black pigment, silica powder, etc. However, in the compositions of this literature, glass powder is not an essential component, and even when a glass component is added, lead oxide is described as the preferred main component, with no disclosure of lead-free black conductive compositions.
Japanese Patent No. 3538387 discloses photocurable conductive compositions having storage stability, providing adhesion on substrates in the different steps of drying, exposure, development and firing, and resolution, and satisfying the need for both sufficient blackness after being fired, and discloses plasma display panels (PDP) with the formation of the underlayer (black layer) electrode circuit using such compositions. The basic first embodiment of these photocurable resin compositions contains (A) tricobalt tetroxide (Co3O4) black microparticles, (B) organic binder, (C) photopolymerizable monomer, and (D) photochemical polymerization initiator. The second embodiment contains (E) inorganic microparticles in addition to the above components. In this literature, with respect to this composition, the inorganic fine particles (E) contain, as needed, a glass powder with a softening point of 400-600° C., conductive powder, heat-resistant black pigment, silica powder, etc. However, the compositions do not contain conductive materials such as ruthenium oxide, and glass powder is not an essential component. Even when a glass component is added, lead oxide is described as the preferred main component, with no disclosure of lead-free black conductive compositions.
Japanese Patent No. 3538408 discloses photocurable conductive compositions having storage stability, providing adhesion on substrates in different steps of drying, exposure, development and firing, and resolution, and satisfying the need for both sufficient conductivity and blackness after being fired, and discloses plasma display panels (PDP) with the formation of the underlayer (black layer) electrode circuit using such compositions. The basic first embodiment of these photocurable resin compositions contains (A) black inorganic microparticles such as inorganic binder-coated ruthenium oxide or another ruthenium compound, copper-chromium black composite oxide, copper-iron black composite oxide, cobalt oxide, etc., (B) organic binder, (C) photopolymerizable monomer, and (D) photochemical polymerization initiator. The photocurable compositions described in this literature are characterized by containing inorganic binder-coated black inorganic microparticles (A). The inorganic binder-coated black inorganic microparticles (A) are obtained by pulverizing molten materials of inorganic microparticles and an inorganic binder, with an inorganic binder having a softening point of 400-600° C. and glass powder with lead oxide as the main component being described as preferred, but with no disclosure of lead-free black conductive compositions.
SUMMARY OF THE INVENTION
The present invention provides novel black conductive compositions to be used in flat panel display devices, for forming black electrodes having a desirable balance of all the preferred electrode properties including electrode pattern properties, blackness, resistance, and storage stability. Furthermore, the present compositions and the electrodes formed therefrom are lead-free.
Disclosed is a black conductive composition comprising, based on the total composition weight percent:
3-50 weight percent of conductive metal oxide particles selected from RuO2, ruthenium polyoxide, and mixtures thereof;
25-85 weight percent organic matter comprising organic polymer binder and organic solvent;
5-70 weight percent of one or more lead-free bismuth glass binders wherein said glass binder comprises, based on weight percent total glass binder composition: 55-85% Bi2O3, 0-20% SiO2, 0-5% Al2O3, 2-20% B2O3, 0-20% ZnO, 0-15% of one or more of oxides selected from BaO, CaO, and SrO; and 0-3% of one or more of oxides selected from Na2O, K2O, Cs2O, Li2O and mixtures thereof;
wherein the softening point of said glass binder is in the range 400-600° C.; and
wherein said composition is characterized by being lead-free or substantially lead-free.
The above composition further comprises conductive metal particles selected from gold, silver, platinum, palladium, copper and mixtures thereof. The above composition may be processed to remove the organic solvent. The invention further concerns a black electrode formed from the above black conductive composition and a flat panel display comprising said electrode.



BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 is an expanded perspective diagram illustrating schematics of the AC PDP device prepared according to one embodiment of the present invention.
FIG. 2 is an explanatory diagram of a series of processes of the method for making the bus electrode and interconnecting electrodes positioned between said bus electrode and a transparent electrode on the same glass substrate: (A) a step for applying the photosensitive thick film composition layer for black electrode formation; (B) a step for applying a photosensitive thick film conductive composition for bus electrode formation; (C) a step for setting an exposed electrode pattern; (D) development step; (E) firing step.
FIG. 3 is an explanatory diagram of a series of processes of the method for making the bus electrode and interconnecting electrodes positioned between said bus electrode and transparent electrode on the same glass substrate: (A) a step for applying the photosensitive thick film composition layer for black electrode formation; (B) a step for setting an exposed electrode pattern; (C) development step (D) firing step (E) a step for applying a photosensitive thick film conductive composition for bus electrode formation; (F) a step for setting an electrode pattern by imagewise exposure of the second bus electrode composition layer; (G) development step; (H) firing step.



EXPLANATION OF SYMBOLS USED IN THE FIGURES
1 transparent electrode
2 address electrode
3 fluorescent material
4 cell barrier
5 front glass substrate
6 rear glass substrate
7 bus conductor electrode
7a exposed part
7b unexposed part
8 dielectric layer
9 protective MgO layer
10 black electrode (photosensitive thick film electrode layer)
10a exposed part
10b unexposed part
11 MgO layer
13 phototool (target)
DETAILED DESCRIPTION OF THE INVENTION
One embodiment of the present invention is directed to black conductive compositions, characterized by being lead-free black conductive compositions comprising, based on the overall composition weight, 3-50 wt % of lead-free conductive metal oxides (oxides with metallic conductivity) made from RuO2, ruthenium polyoxide, or their mixture and 5-70 wt % of a lead-free bismuth-based glass binder having the following characteristics:
(I) Glass Composition














55-85
wt %
Bi2O3


0-20
wt %
SiO2


0-5
wt %
Al2O3


2-20
wt %
B2O3


0-20
wt %
ZnO


0-15
wt %
one or more of oxides selected from BaO,




CaO, and SrO (in the case of an oxide mixture,




the maximum total is up to 15 wt %).


0-3
wt %
one or more of oxides selected from Na2O,




K2O, Cs2O and Li2O (in the case of an oxide mixture,




the maximum total is up to 3 wt %).









(II) Softening Point: 400-600° C.

    
    
        In the present invention, the ruthenium polyoxide is preferably Bi2Ru2O7, CuxBi2-xRuO7, or GdBiRu2O7.
    
    


The present invention is also directed to black electrodes formed from such black conductive compositions. The present invention provides black conductive compositions with an excellent balance of properties such as the adhesive property, appearance and dimensional stability after being fired, resistance and blackness and also concerns black electrodes having such properties.
The lead-free or substantially lead-free black conductive compositions are characterized by comprising, based on the overall composition weight, 3-50 wt % of lead-free conductive metal particles made from RuO2, ruthenium polyoxide, or their mixture, 25-85 wt % organic matter, and 5-70 wt % of a lead-free bismuth glass binder having certain properties.
The black conductive compositions of the present invention are described below.
(A) Conductive Metal Oxide Particles
The black conductive compositions of the present invention comprise (a) conductive metal oxides (oxides with metallic conductivity; RuO2 and or ruthenium polyoxide as the conductive component). The ruthenium polyoxide is a type of pyrochlore, which is a multicomponent compound of Ru+4, Ir+4, or their mixture (M′′) represented by the general formula shown below:

(MxBi2-x)(M′yM′′2-y)O7-z

In the formula, M is selected from a group consisting of yttrium, thallium, indium, cadmium, lead, copper, and rare earth materials; M′ is selected from a group consisting of platinum, titanium, chromium, rhodium, and antimony; M′′ is ruthenium, iridium, or their mixture; x is 0-2, or x≦1 with respect to monovalent copper; y is 0-0.5 but when M′ is rhodium or is more than 1 of platinum, titanium, chromium, rhodium, or antimony, y is 0-1, and z is 0-1 but when M is bivalent lead or cadmium, this is at least equal to about x/2.
The above ruthenium-based pyrochlore oxide is described in detail in U.S. Pat. No. 3,583,931, which is herein incorporated by reference.
Lead containing ruthenium-based pyrochlore oxides may be used in the present invention when a lead-containing system is acceptable. Examples of such oxides include, lead ruthenate Pb2Ru2O6, Pb1.5Bi0.5Ru2O6.5, PbBiRu2O6.75.
Preferred ruthenium polyoxides are bismuth ruthenate Bi2Ru2O7, CuxBi2-xRuO7, or GdBiRu2O7. These materials are readily available in purified form and have no adverse effect on the glass binder. These materials are also stable up to 1000° C. in air and relatively stable even under a reductive atmosphere.
Since the thick film composition of the present invention utilizes a Bi-based glass frit, BiRu pyrochlore, as the conductive oxide component, is particularly useful due to the chemical compatibility of the oxide and frit and decreased expense of the oxide component. For example, although RuO2 functions as a black conductive oxide component, the Ru content in RuO2 is about 70%, thus it is very expensive. BiRu pyrochlore has a Ru content of about 30%, which is one half of RuO2, undergoes no significant chemical reaction with Ag below 600° C., and has good wetting with glass compared with black pigments other than RuO2 and Ru, therefore it is a preferred lead-free black conductive oxide component.
The content of ruthenium oxide and/or ruthenium pyrochlore oxide based on the overall composition weight is 3-50 wt %, preferably 6-30 wt %, more preferably 8-25 wt %, and most preferably 9-20 wt %.
The surface area to weight ratio of the conductive metal oxide(s) of the present invention is in the range of 2 to 20 m2/g. In one embodiment, the range is 5 to 15 m2/g. In a further embodiment, the range of surface area to weight ratio is 6 to 10 m2/g.
The black conductive compositions of the present invention can be used for the black electrode layer in the two layer structure of a bus electrode. Typically, a bus electrode comprises a highly conductive metal layer and a black electrode as its under layer (between the bus electrode and transparent substrate). The compositions of the present invention are suitable for such applications. The black electrode layer of the present invention comprises the conductive metal oxides, as described in (A) above as a necessary component. In addition to the conductive metal oxides of (A) above, the black electrode layer may also, optionally comprise the conductive metal particles described in (B) below. When the black electrode layer comprises the conductive metal particles of (B), a single layer structure can be used (i.e., the highly conductive metal layer and black electrode layer are combined in one layer).
(B) Conductive Metal Particles of the Black Conductive Compositions
As noted above, the black composition of the present invention may optionally, comprise precious metals including gold, silver, platinum, palladium, copper and combinations thereof. Virtually any shape metal powder, including spherical particles and flakes (rods, cones, and plates) may be used in the compositions of the present invention. The preferred metal powders are selected from the group comprising gold, silver, palladium, platinum, copper and combinations thereof. It is preferred that the particles be spherical. It has been found that the dispersion of the invention should not contain a significant amount of conductive metal solids having a particle size of less than 0.2 μm. When particles of this small size are present, it is difficult to adequately obtain complete burnout of the organic medium when the films or layers thereof are fired to remove the organic medium and to effect sintering of the inorganic binder and the metal solids. When the dispersions are used to make thick film pastes, which are usually applied by screen printing, the maximum particle size should not exceed the thickness of the screen. It is preferred that at least 80 percent by weight of the conductive solids fall within the 0.5-10 μm range.
In addition, it is preferred that the surface area to weight ratio of the optional electrically conductive metal particles not exceed 20 m2/g, preferably not exceed 10 m2/g and more preferably not exceed 5 m2/g. When metal particles having a surface area to weight ratio greater than 20 m2/g are used, the sintering characteristics of the accompanying inorganic binder are adversely affected. It is difficult to obtain adequate burnout and blisters may appear.
Often although not required, copper oxide is added to improve adhesion. The copper oxide should be present in the form of finely divided particles, preferably ranging in size from about 0.1 to 5 microns. When present as Cu2O, the copper oxide comprises from about 0.1 to about 3 percent by weight of the total composition, and preferably from about 0.1 to 1.0 percent. Part or all of the Cu2O may be replaced by molar equivalents of CuO.
Additionally, in the compositions of the present invention, non-conductive materials may optionally be added to the black conductive compositions, as needed. Preferred non-conductive materials may be inorganic black pigments that are widely available commercially. In the present invention, the form of the non-conductive materials is not important. When the powder is dispersed to be processed by screen printing, the maximum particle diameter should not exceed the screen thickness.
(C) Glass Binder (Glass Frit)
The glass binder (glass frit) used in the present invention promotes the sintering of conductive component particles. The glass binder used in the present invention is a lead-free, low-melting glass binder.
The glass binder is a lead-free and cadmium-free Bi based amorphous glass. Other lead-free, low-melting glasses are P based or Zn—B based compositions. However, P based glass does not have good water resistance, and Zn—B glass is difficult to obtain in the amorphous state, hence Bi based glasses are preferred. Bi glass can be made to have a relatively low melting point without adding an alkali metal and has little problems in making a powder. In the present invention, Bi glass having the following characteristics is most preferred.
(I) Glass Composition














55-85
wt %
Bi2O3


0-20
wt %
SiO2


0-5
wt %
Al2O3


2-20
wt %
B2O3


0-20
wt %
ZnO


0-15
wt %
one or more of oxides selected from BaO,




CaO, and SrO (in the case of an oxide mixture,




the maximum total is up to 15 wt %).


0-3
wt %
one or more of oxides selected from Na2O,




K2O, Cs2O and Li2O (in the case of an oxide mixture,




the maximum total is up to 3 wt %).









(II) Softening Point: 400-600° C.
In this specification, “softening point” means the softening point determined by differential thermal analysis (DTA).
In the present invention, the glass binder composition and softening point are important characteristics for ensuring a good balance of all the properties of a black electrode are obtained.
When the softening point is below 400° C., melting of the glass may occur while organic materials are decomposed, allowing blisters to occur in the composition. Therefore it is preferred that the softening point of the glass is >400° C. On the other hand, the glass must soften sufficiently at the firing temperature employed. For example, if a firing temperature of 550° C. is used, then the softening point should be <520° C., if the softening point exceeds 520° C. electrode peeling occurs at the corners and properties such as resistance, etc., are affected, compromising the balance of the electrode properties. If a higher firing temperature is used (depending on substrate) glass with softening point up to 600° C. can be used.
The glass binders used in the present invention preferably have a D50 (i.e., the point at which 1⁄2 of the particles are smaller than and 1⁄2 are larger than the specified size) of 0.1-10 μm as measured by a Microtrac. More preferably, the glass binders have a D50 of 0.5 to 1 μm. Usually, in an industrially desirable process, a glass binder is prepared by the mixing and melting of raw materials such as oxides, hydroxides, carbonates, etc., making into a cullet by quenching, mechanical pulverization (wet, dry), then drying in the case of wet pulverization. Thereafter, if needed, classification is carried out to the desired size. It is desirable for the glass binder used in the present invention to have an average particle diameter smaller than the thickness of the black conductive layer to be formed.
A combination of glasses with different softening point may be used in the present invention. High softening point glasses can be combined with low softening point glasses. The proportion of each different softening point glass is determined by the precise balance of the electrode properties required. Some portion of the glass binder may be comprised a glass(s) with a softening point above 600° C.
Based on the overall composition weight, the glass binder content should be 5-70 wt %. When the glass binder content is too small, bonding to the substrate is weak.
The compositions of the present invention may also comprise organic matter. Organic matter is present in the composition in the range of 25-85 wt %, based on total composition. The organic matter included in the present invention may comprise an organic polymer binder and organic solvent. The organic matter may further comprise photoinitiators, photocurable monomers, etc. These are explained below.
(D) Organic Polymer Binders
The polymeric binders are important in the compositions of the present invention and should be selected considering the water-based developability and high resolution. Such requirements are satisfied by the following binders. Such binders may be copolymers and interpolymers (mixed polymers) made from (1) non-acidic comonomers such as C1-10 alkyl acrylates, C1-10 alkyl methacrylates, styrene, substituted styrene, or combinations thereof, and (2) acidic comonomers including an ethylenically unsaturated carboxylic acid in at least 15 wt % of the total polymer weight.
The presence of the acidic comonomers in the compositions is important in the technology of the present invention. With such an acidic functional group, development in an aqueous base such as a 0.4 wt % sodium carbonate aqueous solution is possible. If the acidic comonomer content is less than 15 wt %, the composition may not be washed off completely by the aqueous base. If the acidic comonomer content is above 30%, the composition has low stability under the development conditions and the image area is only partially developed. Suitable acidic comonomers may be ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, etc.; ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, citraconic acid, vinylsuccinic acid, maleic acid, etc., their half esters (hemiesters), as well as sometimes their anhydrides and mixtures. For clean burning under a low-oxygen atmosphere, methacrylic polymers are preferred over acrylic polymers.
When the non-acidic comonomers are alkyl acrylates or alkyl methacrylates described above, the non-acidic comonomer content in the polymeric binders should be at least 50 wt %, preferably 70-75 wt %. When the non-acidic comonomers are styrene or substituted styrene, the non-acidic comonomer content in the polymeric binder should be 50 wt %, with the remaining 50 wt % being an acid anhydride such as maleic anhydride hemiester. The preferred substituted styrene is α-methylstyrene.
While not preferred, the non-acidic portion of the polymeric binder may contain less than about 50 wt % of other non-acidic comonomers substituting the alkyl acrylate, alkyl methacrylate, styrene, or substituted styrene portion of the polymer. For example, they include acrylonitrile, vinyl acetate, and acrylamide. However, in such cases, complete combustion is more difficult, thus such a monomer content should be less than about 25 wt % of the overall polymeric binder weight. Binders may consist of a single copolymer or combinations of copolymers fulfilling various standards described above. In addition to the copolymers described above, other examples include polyolefins such as polyethylene, polypropylene, polybutylene, polyisobutylene, ethylene-propylene copolymer, etc., as well as polyethers such as lower alkylene oxide polymers including polyethylene oxide.
These polymers can be prepared by solution polymerization technology commonly used in the acrylic acid ester polymerization field.
Typically, the acidic acrylic acid ester polymers described above can be obtained by mixing an α- or β-ethylenically unsaturated acid (acidic comonomer) with one or more copolymerizable vinyl monomers (non-acidic comonomer) in an organic solvent having a relatively low boiling point (75-150° C.) to obtain a 10-60% monomer mixture solution, then adding a polymerization catalyst to the monomer, followed by polymerization. The resulting mixture is heated under ambient pressure at the reflux temperature of the solvent. After completion of the polymerization reaction, the resulting acidic polymer solution is cooled to room temperature. A sample is recovered and measured for the polymer viscosity, molecular weight, and acid equivalent.
The acid-containing polymeric binder described above should have a molecular weight below 50,000.
When such compositions are coated by screen printing, the polymeric binder should have a Tg (glass transition temperature) exceeding 60° C.
In general, the organic polymeric binder amounts to 5-45 wt % of the overall dry photopolymerizable layer.
(E) Photoinitiators
Suitable photoinitiators are thermally inert but generate free radicals when exposed to actinic radiation at a temperature below 185° C. These photoinitiators are compounds having two intramolecular rings inside a conjugated carbon ring system and include (un)substituted polynuclear quinines, e.g., 9,10-anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, benz[a]anthracene-7,12-dione, 2,3-naphthacene-5,12-dione, 2-methyl-1,4-naphthoquinone, 1,4-dimethylanthraquinone, 2,3-dimethylanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, retenquinone [transliteration], 7,8,9,10-tetrahydronaphthacene-5,12-dione, and 1,2,3,4-tetrahydrobenz[a]anthracene-7,12-dione. Other useful photoinitiators are described in U.S. Pat. No. 2,760,863 [Of these, some are thermally active at a low temperature of 85° C., such as vicinal ketaldonyl alcohols, e.g., benzoin and pivaloin; acyloin ethers such as benzoin methyl or ethyl ether; α-methylbenzoin, α-allylbenzoin, α-phenylbenzoin, thioxanthone and its derivatives, hydrogen donors, hydrocarbon-substituted aromatic acyloin, etc.]
For initiators, photo-reducible dyes and reducing agents may be used. These are described in U.S. Pat. Nos. 2,850,445, 2,875,047, 3,097,96, 3,074,974, 3,097,097, and 3,145,104 and include phenazine, oxazine, quinones, e.g., Michler's ketone, ethyl Michler's ketone, and benzophenone, as well as hydrogen donors including leuco dyes-2,4,5-triphenylimidazolyl dimmer and their mixtures (U.S. Pat. Nos. 3,427,161, 3,479,185, and 3,549,367). The sensitizers described in U.S. Pat. No. 4,162,162 are useful with the photoinitiators and photoinhibitors. The photoinitiators and photoinitiator systems are present at 0.05-10 wt % based on the overall weight of the dry photopolymerizable layer.
(F) Photocurable Monomer
The photocurable monomer component used in the present invention has at least one polymerizable ethylene group and contains at least one addition-polymerizable ethylenically unsaturated compound.
These compounds initiate polymer formation by free radicals and undergo chain-extending addition polymerization. The monomeric compounds are not gaseous, i.e., having boiling point higher than 100° C., and have plasticizing effects on the organic polymeric binders.
Preferred monomers that can be used alone or in combination with other monomers include t-butyl (meth)acrylate, 1,5-pentanediol di(meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, hexamethylene glycol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, decamethylene glycol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, 2,2-dimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, tripropylene glycol di(meth)acrylate, glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, compounds described in U.S. Pat. No. 3,380,381, 2,2-di(p-hydroxyphanyl)propane di(meth)acrylate, pentaerythritol tetra(meth)acrylate, triethylene glycol diacrylate, polyoxyethylene-1,2-di(p-hydroxyethyl)propane dimethacrylate, bisphenol A di[3-(meth)acryloyloxy-2-hydroxypropyl]ether, bisphenol A di[2-(meth)acryloyloxyethyl]ether, 1,4-butanediol di(3-methacryloyloxy-2-hydroxypropyl)ether, triethylene glycol dimethacrylate, polyoxyporpyltrimethylolpropane triacrylate, butylenes glycol di(meth)acrylate, 1,2,4-butanediol [sic]tri(meth)acrylate, 2,2,4-trimethyl-1,3-pentanediol di(meth)acrylate, 1-phenylethylene 1,2-dimethacrylate, diallyl fumarate, styrene, 1,4-benzenediol dimethacrylate, 1,4-diisopropenylbenzene, and 1,3,5-triisopropenylbenzene [(meth)acrylate means both acrylate and methacrylate].
Useful are ethylenically unsaturated compounds having molecular weights below 300, e.g., an alkylene or polyalkylene glycol diacrylate prepared from an alkylene glycol or polyalkylene glycol, such as a 1-10 ether bond-containing C2-15 alkylene glycol, and those described in U.S. Pat. No. 2,927,022, such as those containing a terminal addition-polymerizable ethylene bond.
Other useful monomers are disclosed in U.S. Pat. No. 5,032,490.
Preferred monomers are polyoxyethylenated trimethylolpropane tri(meth)acrylate, ethylated pentaerythritol acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol monohydroxypentacrylate, and 1,10-decanediol dimethacrylate.
Other preferred monomers are monohydroxypolycaprolactone monoacrylate, polyethylene glycol diacrylate (molecular weight: about 200), and polyethylene glycol dimethacrylate (molecular weight: about 400). The unsaturated monomer component content is 1-20 wt % based on the overall weight of the dry photopolymerizable layer.
(G) Organic Medium
The organic medium is mainly used for the easy coating of dispersions containing a finely pulverized composition on ceramics and other substrates. Thus, first, the organic medium should be capable of dispersing the solid components in a stable manner and, second, the rheological property of the organic medium is to impart good coatability to the dispersion.
In the organic medium, the solvent component that may be a solvent mixture should be selected from those capable of complete dissolution of polymers and other organic components. The solvents are selected from those that are inert (not reactive) with respect to the paste composition components. Solvents are selected from those that have a sufficiently high volatility, thus evaporate well from the dispersion even when coated under ambient pressure at a relatively low temperature, while in the case of the printing process, the volatility should not be too high, causing rapid drying of the paste on the screen at room temperature. Solvents that can be favorably used in the paste compositions should have boiling point below 300° C. under ambient pressure, preferably below 250° C. Such solvents may be aliphatic alcohols or their esters such as acetic acid esters or propionic acid esters; terpenes such pine resin, α- or β-terpineol, or mixtures thereof; ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol esters such as butyl Cellosolve acetate; butyl Carbitol and Carbitol esters such as butyl Carbitol acetate and Carbitol acetate; Texanol (2,2,4-trimethyl-1,3-pentanediol monoisobutyrate), and other suitable solvents.
The compositions of the present invention may also contain additional components described below, in addition to the components described above.
(H) Additional Components
These are dispersants, stabilizers, plasticizers, releases, stripping agents, defoamers, wetting agents, etc., that are well known in the art. Common materials are disclosed in U.S. Pat. No. 5,32,490 herein incorporated by reference.
Uses
The compositions of the present invention may be compounded with photosensitive materials described above to obtain photosensitive compositions. Such photosensitive compositions may be used in various applications, including flat panel display applications.
The black conductive photosensitive compositions may also be formed into films, etc., by the usual pattern-forming technology such as screen printing, chemical etching, or coating process such spinning, dipping, etc.
The black conductive compositions of the present invention may also be utilized in processes for patterning thick film electrically functional patterns using a photosensitive polymer layer. For example, as described in Patent Publication WO 02/03766 A2 to Keusseyan herein incorporated by reference. Keusseyan describes a process for forming a pattern having electrically functional properties on a substrate comprising the steps of: (a) providing a photosensitive layer having a tacky surface disposed on a substrate; (b) providing a transfer sheet comprising a removable support and at least one layer of a thick film composition disposed on the support; (c) image-wise exposing the photosensitive tacky surface to form an imaged layer having unexposed tacky and exposed non-tacky areas; (d) applying the thick film composition of the transfer sheet onto the imaged layer; (e) separating the transfer sheet from the substrate wherein the thick film substantially remains on the support in the exposed non-tacky areas to form a patterned thick film composition; and (f) subjecting the patterned thick film composition to heat thereby forming a patterned article.
When the black conductive compositions of the present invention are used as conductive materials, these compositions may be formed on various substrates, including a dielectric layer or glass substrate (e.g., bare glass panel).
The composition of the present invention may be patterned on a transparent substrate, topped with a photosensitive material, and exposed to UV, etc., from the transparent substrate (back side) to form a photomask.
Flat Panel Display Applications
The present invention includes black electrodes formed from the above black conductive compositions. The black electrodes of the present invention can be favorably used in flat panel display applications, particularly in alternating-current plasma display panel devices. The black electrodes can be formed between the device substrate and conductor electrode array.
In one embodiment, the electrode of the present invention is used in AC PDP applications, as described below. It is understood that the compositions and electrodes of the present invention may be used in other flat panel display applications and their description in AC PDP devices is not intended to be limiting. An example of the black electrodes of the present invention used in an alternating-current plasma display panel is explained below. This description includes two-layer electrodes comprising a black electrode between the substrate and conductor electrode (bus electrode). Also, the method for making an alternating-current plasma display panel device is outlined.
The alternating-current plasma display panel device consists of front and back dielectric substrates with a gap and an electrode array containing parallel first and second electrode composite groups in a discharge space filled with ionizing gas. The first and second electrode composite groups face each other perpendicularly with the discharge space in the middle. A certain electrode pattern is formed on the surface of the dielectric substrate, and a dielectric material is coated on the electrode array on at least one side of the dielectric substrate. In this device, at least the electrode composite on the front dielectric substrate is fitted with the conductor electrode array group connected to the bus conductor on the same substrate, and with the black electrode of the present invention formed between the above substrate and the above conductor electrode array.
FIG. 1 illustrates the black electrode of the present invention in an AC PDP. FIG. 1 shows the AC PDP using the black electrode of the present invention. As shown in FIG. 1, the AC PDP device has the following components: underlying transparent electrode (1) formed on glass substrate (5); black electrode (10) formed on the transparent electrode (1) (the black conductive composition of the present invention is used for the black electrode (10)); bus electrode (7) formed on the black electrode (10) (bus electrode (7) is a photosensitive conductor composition containing conductive metal particles from metals selected from Au, Ag, Pd, Pt and Cu or combinations thereof (this is explained in more detail below)). The black electrode (10) and bus conductor electrode (7) are exposed imagewise by actinic radiation to form a pattern, developed in a basic aqueous solution, and fired at an elevated temperature to remove the organic components and to sinter the inorganic material. The black electrode (10) and bus conductor electrode (7) are patterned using an identical or very similar image. The final result is a fired, highly conductive electrode composite, which appears to be black on the surface of the transparent electrode (1), and when placed on the front glass substrate, reflection of external light is suppressed.
The word ‘black’ used in this specification means a black color with significant visual contrast against a white background. Therefore, the term is not necessarily limited to black which possesses the absence of color. The degree of “blackness” may be measured with a colorimeter to determine an L-value. The L-value represents lightness where 100 is pure white and 0 is pure black. Although shown in FIG. 1, the transparent electrode described below is not necessary in forming the plasma display device of the present invention.
When a transparent electrode is used, SnO2 or ITO is used for forming the transparent electrode (1), by chemical vapor deposition or electro-deposition such as ion sputtering or ion plating. The components of the transparent electrode and method for its formation in the present invention are those of the conventional AC PDP production technology, well known to those in the art.
As shown in FIG. 1, the AC PDP device of the present invention is based on a glass substrate having dielectric coating layer (8) and MgO coating layer (11) over the patterned and fired metallization.
The conductor lines are uniform in line width and are not pitted or broken, have high conductivity, optical clarity and good transparency between lines.
Next, a method for making both a bus electrode and black electrode over the optional transparent electrode on the glass substrate of the front plate of a PDP device is illustrated.
As shown in FIG. 2, the formation method of the one embodiment of the present invention involves a series of processes ((A)-(E)).
(A) A process of applying a black electrode-forming photosensitive thick film composition layer (10) on a transparent electrode (1) formed using SnO2 or ITO according to a conventional method known to those in the art, on the glass substrate (5), then drying the thick film composition layer (10) in a nitrogen or air atmosphere. The black electrode composition is a lead-free black conductive composition of the present invention. (FIG. 2(A)).
(B) Applying to the first applied black electrode composition layer (10) a photosensitive thick film conductor composition (7) for forming the bus electrodes, then drying the thick film composition layer (7) in a nitrogen or air atmosphere. The photosensitive thick film conductive composition is described below. (FIG. 2(B)).
(C) Imagewise exposing the first applied black electrode composition layer (10) and the second bus electrode composition layer (7) to actinic radiation (typically a UV source) through a phototool or target (13) having a shape corresponding to a pattern of the black and bus electrodes arranged in correlation with the transparent electrodes (1), using exposure conditions that yield the correct electrode pattern after development. (FIG. 2(C))
(D) A process of developing the exposed parts (10a, 7a) of the first black conductive composition layer (10) and the second bus electrode composition layer (7) in a basic aqueous solution, such as a 0.4 wt % sodium carbonate aqueous solution or other alkali aqueous solution. This process removes the unexposed parts (10b, 7b) of the layers (10, 7). The exposed parts (10a, 7a) remain (FIG. 2(D)). The developed product is then dried.
(E) After process, (D), the parts are then fired at a temperature of 450-650° C., depending upon the substrate material, to sinter the inorganic binder and conductive components (FIG. 2(E)).
The formation method of the second embodiment of the present invention is explained below with FIG. 3. For convenience, the numbers assigned for each part of FIG. 3 are same as FIG. 2. The method of the second embodiment involves a series of processes (A′-H′).
A′. A process of applying a black electrode-forming photosensitive thick film composition layer (10) on a transparent electrode (1) formed using SnO2 or ITO according to a conventional method known to those in the art, on the glass substrate (5), then drying the thick film composition layer (10) in a nitrogen or air atmosphere. The black electrode composition is a lead-free black conductive composition of the present invention. (FIG. 3(A)).
B′. Imagewise exposing the first applied black electrode composition layer (10) to actinic radiation (typically a UV source) through a phototool or target (13) having a shape corresponding to a pattern of the black electrodes arranged in correlation with the transparent electrodes (1), using exposure conditions that yield the correct black electrode pattern after development. (FIG. 3(B)).
C′. A process of developing the exposed part (10a) of the first black conductive composition layer (10) in a basic aqueous solution such as a 0.4 wt % sodium carbonate aqueous solution or other alkali aqueous solution for removal of the unexposed parts (10b) of the layers (10) (FIG. 3(C)). The developed product is then dried.
D′. After process, (C′), the parts are then fired at a temperature of 450-650° C., depending upon the substrate material, to sinter the inorganic binder and conductive components (FIG. 3(D)).
E′. A process of applying the bus electrode-forming photosensitive thick film composition layer (7) to the black electrode (10a) according to the fired and patterned part (10a) of the first photosensitive thick film composition layer (10), then drying in a nitrogen or air atmosphere. (FIG. 3(E)). The photosensitive thick film conductor composition is described below.
F′. Imagewise exposing the second applied bus electrode composition layer (7) to actinic radiation (typically a UV source) through a phototool or target (13) having a shape corresponding to a pattern of the bus electrodes arranged in correlation with the transparent electrodes (1) and black electrode (10a), using exposure conditions that yield the correct electrode pattern after development. (FIG. 3(F)).
G′. A process of developing the exposed part (7a) of the second bus conductive composition layer (7) in a basic aqueous solution such as a 0.4 wt % sodium carbonate aqueous solution or other alkali aqueous solution for removal of the unexposed parts (7b) of the layers (7) (FIG. 3(G)). The developed product is then dried.
H′. After process, (G′), the parts are then fired at a temperature of 450-650° C., depending upon the substrate material, to sinter the inorganic binder and conductive components (FIG. 3(H)).
The third embodiment (not shown) involves a series of processes ((i)-(v)) shown below. This embodiment is particularly useful in the formation of single layer electrodes.
(i) The process of loading a black electrode composition on a substrate. This black electrode composition is the black conductive composition of the present invention described above.
(ii) The process of loading a photosensitive conductive composition on a substrate. This photosensitive conductive composition is described below.
(iii) The process of setting an electrode pattern by imagewise exposure of the black composition and conductive composition by actinic radiation.
(iv) The process of developing the exposed black composition and conductive composition by a basic aqueous solution for removal of the area not exposed to actinic radiation.
(v) The process of firing the developed conductive composition.
The front glass substrate assembly formed as described above can be used for a AC PDP. For example, referring back to FIG. 1, after forming the transparent electrode (1) in relation to the black electrode (10) and bus electrode (7) on the front glass substrate (5), the front glass substrate assembly is covered with dielectric layer (8), then coated with MgO layer (11). Next, the front glass substrate (5) is combined with rear glass substrate (6). A number of display cells screen printed with phosphor with cell barrier (4) formation are set on the rear glass (6). The electrode formed on the front substrate assembly is perpendicular to the address electrode formed on the rear glass substrate. The discharge space formed between the front glass substrate (5) and rear glass substrate (6) is sealed with a glass seal and at the same time a mixed discharge gas is sealed into the space. The AC PDP device is thus assembled.
Next, bus conductive compositions for bus electrodes are explained below.
The bus conductive compositions used in the present invention may be photosensitive thick film conductive compositions available commercially. As noted above, the bus conductive composition comprises (a) conductive metal particles of at least one metal selected from Au, Ag, Pd, Pt, and Cu and combinations thereof; (b) at least one inorganic binder; (c) photoinitiator; and (d) photocurable monomer. In one embodiment of the present invention, the bus conductive composition comprises Ag.
The conductive phase is the main component of the above composition, typically comprising silver particles with a particle diameter within the range of 0.05-20 μm (microns) in a random or thin flake shape. The bus conductive composition is herein described with reference to one embodiment comprising silver particles, but is not intended to be limiting. When a UV-polymerizable medium is used together with the composition, the silver particles should have a particle diameter within the range of 0.3-10μ. Preferred compositions should contain 65-75 wt % of silver particles based on the overall thick film paste.
The silver conductive composition for forming a bus electrode may also contain 0-10 wt % of a glass binder and/or 0-10 wt % of refractory materials that do not form glass or a precursor as needed, in addition to Ag. Examples of the glass binder include lead-free glass binders described in the Claims of the present invention. Refractory materials that do not form glass and precursors are, e.g., alumina, copper oxide, gadolinium oxide, tantalum oxide, niobium oxide, titanium oxide, zirconium oxide, cobalt iron chromium oxide, aluminum, copper, various commercially available inorganic pigments, etc.
Objectives for adding the second, third, and more inorganic additives in addition to such main components are for control of the pattern shape, suppression or promotion of sintering during firing, adhesive property retention, control of the main-metal component diffusion, inhibition of discoloration near the bus electrode, control of resistance, control of the thermal expansion coefficient, mechanical strength retention, etc. The type and amount are selected as needed within the range of having no significant adverse effects on the basic performance.
Furthermore, the silver conductive compositions may also contain 10-30 wt % of a photosensitive medium in which the above particulate materials are dispersed. Such a photosensitive medium may be polymethyl methacrylate and a polyfunctional monomer solution. This monomer is selected from those with a low volatility for minimizing evaporation during the silver conductive composition paste preparation and printing/drying process before the UV curing. The photosensitive medium also contains a solvent and UV initiator. The preferred UV polymerizable medium includes a polymer based on methyl methacrylate/ethyl acrylate in a 95/5 ratio (weight based). The silver conductive composition described above has a viscosity of 10-200 Pa-s, for a free-flowing paste.
Suitable solvents for such a medium are, but not limited to, butyl Carbitol acetate, Texanol® and β-terpineol. Additional solvents that may be useful include those listed in Section (G) Organic Medium, above. Such a medium may be treated with dispersants, stabilizers, etc.
Preparation of Photosensitive Wet-Developable Pastes
(A) Preparation of Organic Materials
The solvent and acrylic polymer were mixed, stirred, and heated to 100° C. to complete dissolution of the binder polymer. The resulting solution was cooled to 80° C., treated with the remaining organic components, stirred to complete the dissolution of all solids, passed through a 325-mesh filter screen, and cooled.
(B) Preparation of Paste
The paste was prepared by mixing an organic carrier, one or more monomers, and other organic components in a mixing vessel under yellow light. The inorganic materials were then added to the mixture of organic components. The entire composition was then mixed until the inorganic particles were wetted with the organic material. This mixture was roll-milled using a 3-roll mill. The resulting paste was used as obtained or was passed through a 635-mesh filter screen. At this point, the paste viscosity was adjusted by carriers or solvents to a viscosity most suitable for optimum processing.
Care was taken to avoid dirt contamination in the process of preparing paste compositions and in preparing parts, since such contamination can lead to defects.
(C) Preparation Conditions
(1) Formation of Black Electrode

    
    
        Depending on the composition and desired thickness after drying, the paste was applied to the glass substrate by screen printing, using a 200-400 mesh screen. The example black pastes were applied to the glass substrates by screen printing, using a 350 mesh polyester screen. Parts to be tested as a 2-layer structure were prepared on a glass substrate on which a transparent electrode (thin film ITO) has been formed. Parts to be tested as a single layer (black only) structure were prepared on a glass substrate without the ITO film. Parts were then dried at 80° C. for 20 min in a hot-air circulation oven to form a black electrode with a dry film thickness of 2-6 μm.
        Parts to be tested as a single layer (black only) structure were then fired (see process 5).
        Parts to be tested as a 2-layer structure were then processed as shown below (see process 2-5).
    
    


(2) Formation of Bus Conductive Electrode

    
    
        Next, a photoimage-forming Ag conductive paste was overlaid by screen printing using a 325 stainless steel mesh screen. This photoimage-forming Ag conductive paste was a photosensitive Ag paste containing 2 wt % of bismuth glass frit B in the paste and 64-72wt % of Ag powder (average particle diameter: 1.3-2.0 μm). In the examples below, 4 Ag conductive pastes with compositions described later (Ag paste A, Ag paste B, Ag paste C, Ag paste D) were used. These 4 Ag conductive pastes gave essentially the same properties as bus conductor electrodes.
    
    


This part was dried again at a temperature of 80° C. for 20 min. The dry film thickness was 6-10 μm. The dry thickness for the two-layer structure was 10-16 μm.
(3) UV Pattern Exposure
The two-layer parts were exposed through a phototool using a collimated UV light source Illumination: 5-20 mW/cm2. Exposure energy: 400 mj/cm2; off contact exposure, mask-coating gap: 150 μm).
(4) Development
The exposed part was placed on a conveyor, then led into a spray developer containing a 0.4 wt % sodium carbonate aqueous solution as the developer solution. The developer solution temperature was maintained at 30° C., and sprayed at 10-20 psi. The part was subjected to a development time of 20 seconds (corresponding to 3-4 times time to clean—TTC). The developed part was dried by blowing off the excess water in a forced air stream.
(5) Firing
The dried parts were then fired in a belt furnace in an air atmosphere using a 2.5 hr. profile, reaching a peak temperature of 550° C.
EXAMPLES
In the examples illustrated below, the constitutional components are shown in wt %.
Test Procedures
Dried Black Thickness
The dry film thickness of the black electrode was measured at four different points using a contact profilometer, such as a Tencor Alpha Step 2000.
Dried Ag/Black Thickness
The Ag electrode was coated on the dried film of the black electrode, then dried. The dry film thickness of the Ag/Black composite layer was measured using the same method as black electrode above.
Line Resolution
Imaged samples were inspected using a zoom microscope at a minimum magnification of 20× with 10× oculars. The finest group of lines, which are completely intact without any shorts (connections between the lines) or opens (complete breaks in a line), is the stated line resolution for that sample.
4 mil Line Thickness
The fired film thickness was measured on the 4 mil width lines that were used to measure resistivity. Measurement was made using a contact profilometer.
4 mil Line Edge Curl
When the 4 mil line film thickness was measured, the devil's horn-shaped protrusion of the edges is observed in some cases, and the length of this devil's horn is called edge curl. With a large edge curl, the effective film thickness is decreased by the edge curl after the transparent dielectric material is formed by printing, lamination, or coating, then fired; this causes bubble inclusion, leading to the possibility of dielectric breakdown, thus edge curl is not desired. No edge curl, i.e., edge curl being 0 μm, is most desirable. It is known that even with most well-used lead-containing conductive compositions, the edge curl is about 1-3 μm.
Peeling
The degree of pattern corner lifting after being fired is observed under a microscope and classified into levels of none, slight (or low), medium, med-high (or medium-high), and high. With lead-containing conductive compositions (Pb type material) that are the most well used currently, a slight level of corner lifting is observed, while no corner lifting is most desirable.
L Value Ag/Black Two Layer
After firing, the blackness viewed from the back of the glass substrate is measured mechanically. For blackness, the color (L*) was measured using the optical sensor SZ and color measurement system Σ 80 of Nippon Denshoku Kogyo with calibration using a standard white plate, with 0 being pure black and 100 pure white. Alternatively, color measurements were done using a Minolta CR-300 calorimeter, calibrated with multiple standards (white, red, and black). Color was measured on the CIE L*a*b. L* represents lightness where 100 is pure white and 0 is pure black.
L Value of Single Layer (Black Only)
An ITO film-free insulation glass substrate was coated with a black electrode as in (1) above and dried. Omitting each of the processes (2), (3), and (4), the dry black electrode thus obtained is fired under the same conditions of the process of (5) to form a single solid fired black electrode layer. After the firing, the blackness viewed from the back of the glass substrate was measured by the color meter of Nippon Denshoku or the Minolta CR-300 calorimeter under the conditions used for the above L value Ag/black two layer, with 0 being pure black and 100 pure white.
Black Resistance (ohm)
In this evaluation the resistance of the black electrode was measured. This method is used to confirm the conductive property of the fired black layer. Using the test part described above (L value of single layer), the resistance of the black electrode fired film was measured using a resistance meter with a probe distance of about 4 cm. Using this equipment, the maximum resistance that can be measured is 1 Gohm.
Black/Ag Two Layers Resistivity (m ohm/sq@5 μm)
This is the sheet resistance value (mΩ/sq) per unit of fired film thickness (5 μm). This is measured on the 4 mil lines. This value equates to 2 times the so-called specific resistance (μΩ-cm). When the prior art lead-containing conductive composition (Pb type Commercial Product Number DC243 paste available from E. I. du Pont de Nemours and Company) and Ag electrode (DC206) are used, this value is known to be about 11-13 mohm/sq@5 μm. The lower this value, the better.
GLOSSARY
Ts: softening point determined in differential thermal analysis (DTA)

    
    
        Compositions of each component used in the examples of this specification are given below.
    
    


Organic Components

    
    
        Organic binder A
        Monomer A: monomer TMPEOTA (trimethylolpropane ethoxytriacrylate)
        Solvent A: solvent, Texanol
    
    


Organic additive A: additive, malonic acid
Organic additive B: additive BHT
Organic binder B
Monomer B: oligomer, CN2271, polyester acrylate oligomer, available from Sartomer Co., Inc. in Pennsylvania

    
    
        Solvent A: solvent, Texanol
        Organic additive C: additive, CBT (1 H-benzotriazolecarboxylic acid)
    
    


Organic Binder A














Acrylic
34.78
Acrylic resin (Carboset XPD1234), methyl


Resin A

methacrylate 75%, methacrylic acid 25%,




Mx = ~7000, Tg = 120° C., acid value = 164


Solvent A
46.64
Texanol


Resin B
1.46
PVP/VA, vinylpyrrolidone-vinyl acetate




copolymer


Initiator A
8.78
Photoinitiator, DETX (diethylthioxanthone)


Initiator B
8.28
Photoinitiator, EDAB (ethyl 4-




dimethylaminobenzoate)


Inhibitor A
0.06
Light stabilizer TAOBN (1,4,4-trimethyl-2,3-




diazabicyclo[3.2.2]non-2-ene-N,N′-dioxide









Organic Binder B














Acrylic
29.02
Acrylic resin


Resin B

MMA/ETHYL ACRYLATE/BMA/MAA




copolymer. Mw = ~30000, acid value = ~130


Solvent A
33.85
Texanol


Initiator A
8.78
Photoinitiator, DETX (diethylthioxanthone)


Initiator B
8.28
Photoinitiator, EDAB




(ethyl 4-dimethylaminobenzoate)


Inhibitor A
0.07
Light stabilizer TAOBN (1,4,4-trimethyl-2,3-




diazabicyclo[3.2.2]non-2-ene-N,N′-dioxide









Ag Paste Component
1. Ag Paste A and B Formulation (wt %)













Ag
Ag




paste A
paste B
Description


















23.27
23.27
Organic





Binder C


6.43
6.72
Organic




Binder D


1.96
1.89
Monomer A
Monomer, TMPEOTA





(trimethylolpropane ethoxytriacrylate)


1.96
1.89
Monomer C
Oligomer, product of BASF Co.,





Laromer LR8967 (polyester acrylate





oligomer)


0.15
0.15
Organic
Additive, malonic acid




Additive A


2.17
2.09
Bi Frit B


64.06

Ag
D50: 1.3 um spherical powder




powder A



63.99
Ag
D50: 2.0 um spherical powder




powder B









Organic Binder













Binder
Binder




C
D
Description
Chemical Name


















69.16
68.81
Solvent A
Texanol


26.05
25.92
Acrylic
Acrylic resin




Resin B
MMA/ETHYL ACRYLATE/BMA/





MAA copolymer, Mw = ~30000,





acid value = ~130


2.37
0.5
Initiator A
Photoinitiator, DETX





(diethylthioxanthone)


2.37

Initiator B
Photoinitiator, EDAB (ethyl 4-





dimethylaminobenzoate)



2.36
Initiator C
Irgacure 907 (Ciba), 2-methyl-1-[4-





(methylthio)phenyl]-2-





morpholinopropan-1-one



2.36
Initiator D
Irgacure 369 (Ciba), 2-benzyl-2-





dimethylamino-1-(4-





morpholinophenyl)butanone-1


0.05
0.05
Inhibitor A
Stabilizer, TAOBN (1,4,4-trimethyl-





2,3-diazabicyclo[3.2.2]non-2-ene-





N,N′-dioxide)









2. Ag Paste C and D Formulation (wt %)













Ag
Ag




paste C
paste D


















18.65
18.65
Organic





Binder E


3.97
3.97
Monomer A
Monomer, TMPEOTA





(trimethylolpropane ethoxytriacrylate)


4
4
Solvent A
Texanol


0.15
0.15
Organic
Additive CBT




Additive C
(1H-benzotriazolecarboxylic acid)


0.5
0.5
Bi Frit B


71.34

Ag powder A
D50: 1.3 um spherical powder



71.34
Ag powder B
D50: 2.0 um spherical powder


0.5
0.5
Additive D
BYK Chemie BYK*085





(Poly-methyl-alkyl-siloxane)









Organic Binder E (N97M)











Wt %
















52.48
Texanol


36.01
Acrylic resin



MMA/ETHYL ACRYLATE/BMA/MAA copolymer,



Mw = ~30000, acid value = ~130


5.72
Irgacure 907 (Ciba), 2-methyl-1-[4-(methylthio)phenyl]-2-



morpholinopropan-1-one


5.72
Irgacure 651 (Ciba), 2,2-dimethoxy-1,2-diphenylethan-1-one


0.07
Stabilizer, TAOBN (1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-



2-ene-N,N′-dioxide)









Glass Frit Compositions in Weight Percent Total Glass Composition



















Glass











Name
Pb Frit A
Pb Frit B
Bi Frit A
Bi Frit B
Bi Frit C
Bi Frit D
Bi Frit E
Bi Frit F
Bi Frit G
























PbO
77
62.1









Bi2O3


70.0
71.8
69.8
67.5
56.8
65
58.8


SiO2
9.1
30.8
1.5
1.0
7.1
11.5
18.2
5
16.2


Al2O3
1.4
2.6
0.5
0.5
2.1
1.5
2.3

2.3


B2O3
12.5
1.8
10.0
9.6
8.4
7.5
9.1
18
9.1


ZnO

2.7
14.0
14.4
12.0
11.0
12.7

12.7


BaO


4.0
2.9
0.5
1.0
0.9
12
0.9


Total
100
100
100
100
100
100
100
100
100


D50 (um)
0.9
0.9
0.8
0.6
0.9
0.9
0.9
1
0.9


Ts (DTA)
440
597
451
448
501
534
568
551
556









Ru Mixture A used in the examples is identified as Pb0.75Bi0.25RuO3 pyrochlore with a surface area per weight ratio of 11 m2/g. Ru Mixture B in the examples is identified as BiRuO3 pyrochlore with a surface area per weight ratio of 10 m2/g.
For the examples illustrated below, the electrode preparation conditions are as shown in Section (C) Preparation Conditions, (1)-(5), above.
Application Examples 1-6, Controls 1-2
The Ag conductive paste used in these examples was Ag paste A.
BiRu pyrochlore powder (Ru mixture B, specific surface area per weight ratio: 11 m2/g) was combined with Bi glass powder having a different softening point, and paste samples of the compositions shown in Table 1 were prepared. Using the above processes (1)-(5), bus electrode-black electrode two layer test parts were prepared and investigated for various properties.















TABLE 1





Ingredients
Control 1
Control 2
Example 1
Example 2
Example 3
Example 4
Example 5
Example 6























Organic binder A
28.8
28.31
25.16
25.16
26.09
26.89
26.89
26.89


monomer A
7.2
7.08
6.29
6.29
6.52
6.72
6.72
6.72


solvent A
5.27
5.18
4.6
4.6
4.77
4.92
4.92
4.92


Organic Additive A
0.96
0.94
0.84
0.84
0.87
0.9
0.9
0.9


Organic Additive B
0.19
0.19
0.17
0.17
0.17
0.18
0.18
0.18


Pb glass frit A
16.32
16.04


Pb glass frit B
24
23.59


Bi frit A



46.34


Bi frit B


46.34


Bi frit C




44.36


Bi frit D





42.66


Bi frit E






42.66


Bi frit F







42.66


Ru mixture A
17.26


Ru mixture B

18.67
16.6
16.6
17.22
17.73
17.73
17.73









The Bi glasses in these black electrode examples were amorphous glass powders with a softening point in the range of 448-568° C. The photosensitive Ag paste used for the upper layer Ag electrode contained 60% of Ag powder (average particle diameter: about 2 μm) and 2% of Bi frit B having the lowest softening point of the glass powders selected.
Results are given in Table 2.
















TABLE 2







Control 1
Control 2
Example 1
Example 2
Example 3
Example 4
Example 5
Example 6
























Conductive
PbBiRu
BiRu
BiRu
BiRu
BiRu
BiRu
BiRu
BiRu


Frit Ts (DTA)
540 (calc)
540 (calc)
448
478
501
534
568
551


Dried Black thickness/um
6.0
6.4
6.0
5.8
5.8
6.0
6.2
7.3


Dried Ag/Black thickness/um
12.8
13.3
12.9
13.0
13.0
13.1
13.3
13.5


Line Resolution (um)
40
40
40
30
30
40
40
40


4 mil line thickness/um
6.0
7.0
6.0
6.0
6.5
7.0
6.0
7.0


4 mil line edge curl/um
0.0
3.8
2.0
2.0
1.0
2.0
Blister
2.0


Peeling
medium
slight
none
medium
slight
medium–large
medium–large
medium–










large


L value Ag/Black two layer
8.9
8.99
6.68
12.15
14.4
13.59
9.07
9.56


L value of black 1 layer
3.97
3.88
2.52
2.61
3.7
3.61
19.6
4.87


Resistivity/mohm/sq@5 um
9.9
14.3
13.8
15.7
16.5
18.8
20.1
21.6


Black resistance (ohm)
182k
171k
267k
230k
225k
203k
240k
217k









It was learned that compared with controls 1 and 2 (the lead-containing compositions), Examples 1-3 (which used lower softening point frit) performed well at this firing temperature (550° C.), i.e. practical black electrodes were formed. Examples 4-6 (which used higher softening point frit) did not perform so well in all aspects of testing. If examples 4-6 had been fired at a higher temperature, such as 600° C., they would have shown better performance.
Application Examples 7-13. Control 1a
The Ag conductive paste used in these examples was Ag paste A.
The Bi frit B showed good results in Application Examples 1-3; two types of glass with high softening points, judged as difficult to use alone, were used in weight ratios of 75/25, 50/50, and 25/75 wt %, with Bi frit B, to obtain black electrode samples (see Table 3). A two-layer evaluation was made in combination with the Ag electrode of Application Examples 1-3. A test was also conducted on a paste containing a Bi glass with a softening point near 550° C. (Example 7).















TABLE 3










Example
Example
Example
Example



Example 7
Example 8
Example 9
10
11
12
13

























75%
50%
25%
75%
50%
25%




BT26025
BT26025
BT26025
BT26025
BT26025
BT26025




25%
50%
75%
25%
50%
75%




BD19
BD19
BD19
BT192
BT192
BT192


Ingredient


Organic
27.2
25.9
26.3
26.8
25.9
26.3
26.8


binder B


monomer B
6.8
6.46
6.57
6.69
6.46
6.57
6.69


solvent A
5
4.73
4.81
4.9
4.73
4.81
4.9


Bi frit B

35.7
24.2
12.3
35.7
24.2
12.3


Bi frit D

10.2
20.8
31.7


Bi frit G
43


Bi frit E




10.2
20.8
31.7


Ru mixture B
18
17
17.3
17.6
17
17.3
17.6



100
100
100
100
100
100
100









Results
Results are shown in Table 4. Table 4 also shows measurement results for a lead-containing black conductive composition similar to the above control 1 (control 1A).
















TABLE 4










Example
Example
Example
Example
control 1A



Example 7
Example 8
Example 9
10
11
12
13
(Pb type)
























Conductive
BiRu
BiRu
BiRu
BiRu
BiRu
BiRu
BiRu
PbBiRu


Frit Ts (DTA)
556
448/534
448/534
448/534
448/568
448/568
448/568
540 (calc)


Dried Black thickness/um
4.0
4.2
4.1
4.0
3.9
3.8
4.0
5.0


Dried Ag/Black thickness/um
11.0
11.0
11.3
11.0
10.5
11.0
11.1
12.5


Line Resolution (um)
40
40
40
30
30
40
40
40


4 mil line thickness/um
5.5
5.5
5.6
6.0
5.5
5.4
5.5
5.0


4 mil line edge curl/um
2.6
2.5
2.5
4.3
3.3
2.5
2.4
1.1


Peeling
medium
medium
medium
med–high
med–high
med–high
medium
low


L value Ag/Black two layer
15.0
11.1
13.1
15.1
11.8
14.1
15.3
9.6


L value of black 1 layer
14.5
4.2
4.4
5.0
4.7
4.4
13.8
6.9


Resistivity/mohm/sq@5 um
22.4
22.6
17.6
21.5
18.0
15.7
20.1
11.5


Black resistance (ohm)
360k
366k
397k
380k
412k
407k
380k
430k









This data shows that low-softening-point glass can be mixed with different types of second Bi glass (high softening point), and give satisfactory performance. Varying the level of high and low softening point glass frits is an effective way achieving a desired balance of electrode properties. While some frit combinations did not perform so well at this firing temperature, at other firing temperatures, these frit combinations could perform well.
Application Examples 14-21 Control 1b
The Ag conductive paste used in these examples was Ag paste A.
In these examples, the BiRu pyrochlore level was varied from 13-25 volume percent of the inorganic content in the total composition. Examples 14-17 used Bi Frit B and examples 18-21 used high softening Bi Frit D. Compositions are given in Table 5.















TABLE 5






Example
Example
Example
Example
Example
Example
Example
Example


sample
14
15
16
17
18
19
20
21








BiRu
BiRu
BiRu
BiRu
BiRu
BiRu
BiRu
BiRu



25 vol %
21 vol %
17 vol %
13 vol %
25 vol %
21 vol %
17 vol %
13 vol %


Ingredient


Organic
24.95
25.16
25.36
25.59
26.6
26.34
27.28
27.62


binder A


monomer A
6.24
6.29
6.34
6.39
6.65
6.74
6.82
6.91


solvent A
4.57
4.6
4.64
4.68
4.87
5.5
4.99
5.06


Organic
0.83
0.84
0.85
0.85
0.89
0.9
0.91
0.92


Additive A


Organic
0.16
0.17
0.17
0.17
0.18
0.18
0.18
0.18


Additive B


Bi frit B
43.59
46.33
49.03
51.85


Bi frit D




39.84
42.52
45.19
48


Ru mixture B
19.66
16.61
13.61
10.47
20.97
17.79
14.63
11.31



100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0









Results
Results are given in Table 6. Table 6 also shows measurement results for a lead-containing black conductive composition similar to the above control 1 (control 1B).

















TABLE 6







Example
Example
Example
Example
Example
Example
Example
Example
control 1B



14
15
16
17
18
19
20
21
(Pb type)

























Conductive
BiRu
BiRu
BiRu
BiRu
BiRu
BiRu
BiRu
BiRu
PbBiRu



25 vol %
21 vol %
17 vol %
13 vol %
25 vol %
21 vol %
17 vol %
13 vol %


Frit Ts (DTA)
448
448
448
448
534
534
534
534
540 (calc)


Dried Black
4.5
5.0
5.0
4.9
5.3
5.3
5.0
5.2
5.0


thickness um


Dried Ag/Black
12.4
13.0
12.5
12.9
13.1
12.9
12.7
12.9
12.9


thickness/um


Line Resolution
40
40
40
40
40
40
40
40
40


(um)


4 mil line thickness/
5.8
6.0
6.0
6.0
6.5
7.0
6.3
6.3
7.5


um


4 mil line edge curl/
2.5
2.8
2.8
2.8
3.8
4.5
4.3
3.5
2.5


um


Peeling
medium
medium
medium
med–high
low
med–high
med/high
med/high
none


L value Ag/Black
5.5
7.0
11.7
15.6
13.7
15.3
16.0
19.2
9.2


two layer


L value of black 1
3.7
3.0
5.2
9.1
4.4
5.1
8.7
18.4
5.4


layer


Resistivity/
14.1
12.9
11.0
15.8
19.4
20.3
16.8
17.2
9.3


mohm/sq@5 um


Black Resistance
86k
190k
430k
2M
29k
43k
204k
9.7M
754k


(Ohm)









Compositions based on Bi frit B performed better than compositions based on Bi frit D under these test conditions (firing at 550° C.). A higher firing temperature would be more appropriate for those compositions based on Bi frit D. The general tendency with variation (decrease) of the black conductive component content is that the L value increases and the resistance of the black conductive layer increases.
Application Examples 22-27 Control 1c
In these examples, Ag conductive pastes based on Ag paste A were prepared with different binder levels (0, 1 and 2 wt % Bi frit B), then evaluated in a two layer structure with black example pastes 15 or 19 (see above).
Results
Results are given in Table 7. The table also shows measurement results for a lead-containing black conductive composition similar to the above control 1 (control 1C).














TABLE 7








Example
Example
Example
Example
Example
Example
control 1C



22
23
24
25
26
27
(Pb type)





Glass binder % in Ag
0%
1%
2%
0%
1%
2%
2%


(upper layer)





Black Conductor
Example
Example
Example
Example
Example
Example


Composition
15
15
15
19
19
19
Control 1c





Frit Ts (DTA)
448
448
448
534
534
534
540 (calc)


Dried Black thickness/um
5.0
5.0
5.0
5.3
5.3
5.3
5.0


Dried Ag/Black thickness/um
13.0
12.0
13.0
12.9
12.5
12.9
12.9


Line Resolution (um)
40
40
40
40
40
40
40


4 mil line thickness/um
5.8
5.3
6.0
6.4
6.5
7.0
7.5


4 mil line edge curl/um
2.3
2.5
2.8
1.8
3.5
4.5
2.5


Peeling
medium
medium
medium
low
medium
med–high
none


L value Ag/Black two layer
9.0
8.0
7.0
11.5
14.1
15.3
9.2


Resistivity/mohm/sq@5 um
11.5
10.7
12.9
8.2
16.5
20.3
9.3









The black electrode (example 15) using Bi frit B was not affected by changing the glass binder content in the Ag electrode. On the other hand, the electrodes formed from black electrode compositions using Bi frit D, which is a high-softening-point glass frit, were affected by the glass binder content in the Ag electrodes. Therefore, in the case of forming two-layer electrodes, not only the black conductive compositions, but also the high conduction layer (bus electrode) composition is important.
Application Examples 28-34 
The Ag conductor paste used in these examples was Ag paste B.
An evaluation was made for effects of the specific surface area per weight ratio of BiRu pyrochlore used as the black conductive component. Using BiRu pyrochlore with different specific surface area per weight ratios (3.25-9.02 m2/g), compositions shown in Table 8 were prepared.














TABLE 8






Example
Example
Example
Example
Example
Example
Example


Sample
28
29
30
31
32
33
34






















Ingredient









Organic binder A
27.5
27.5
27.5
27.5
27.5
27.5
27.5


monomer A
6
6
6
6
6
6
6


solvent A
4.55
4.55
4.55
4.55
4.55
4.55
4.55


Organic Additive A
0.8
0.8
0.8
0.8
0.8
0.8
0.8


Organic Additive B
0.15
0.15
0.15
0.15
0.15
0.15
0.15


Bi frit B
47
47
47
47
47
47
47


Ru mixture B


SA = 3.25 m2/g
14


SA = 4.04

14


SA = 4.91


14


SA = 5.71



14


SA = 6.61




14


SA = 7.86





14


SA = 9.02






14



100
100
100
100
100
100
100









Results
Results are shown in Table 9.















TABLE 9







Example
Example
Example
Example
Example
Example
Example



28
29
30
31
32
33
34























Conductive
BiRu
BiRu
BiRu
BiRu
BiRu
BiRu
BiRu


Conductive Specific Surface Area
3.25
4.04
4.91
5.71
6.61
7.86
9.02


to weight ratio m2/g


Frit Ts (DTA)
448
448
448
448
448
448
448


Dried Black thickness/um
3.9
4.2
3.6
3.6
4.2
3.5
4.6


Dried Ag/Black thickness/um
13.1
12.6
13.1
13.2
12.7
12.9
13.1


Line resolution (um)
30
30
30
30
30
30
30


4 mil line thickness/um
6.7
7.0
6.2
5.7
5.8
5.7
6.3


4 mil line edge curl/um
2.0
2.5
1.8
2.5
2.0
2.0
2.0


Peeling
slight
slight
slight
slight
slight
medium
medium


L value Ag/Black two layer
23.2
18.2
16.9
16.6
18.0
16.2
13.9


L value of black 1 layer
19.2
14.6
11.8
10.0
10.1
9.8
8.9


Black/Ag resistivity/
13.4
13.2
13.1
13.4
14.1
13.9
14.8


mohm/sq@5 um


Black resistance (ohm)
>1G
>1G
>1G
10M
740K
380K
210K









With a BiRu pyrochlore specific surface area per weight ratio below 4.91 m2/g, black resistance becomes >1 Gohm, with an increased L value. To reduce L value and black resistance (with reduced specific surface area per weight ratio pyrochlore) more pyrochlore content is required. Therefore, in the present invention, a surface area per weight ratio above 5 m2/g is preferred, but not essential.
Application Examples 35-38 
The Ag conductive paste used in these examples was Ag paste C.
An investigation was made on the effects of the inorganic solids content in the black electrode pastes. The inorganic solids content in the black electrode paste was varied at 60-15 wt % of the total paste composition. The BiRu pyrochlore/glass ratio was fixed at about 0.3. Compositions are shown in Table 10.












TABLE 10







Example
Example
Example
Example



35
36
37
38




















% solids
60
45
30
15


Ingredient


Organic
27.6
37.86
48.44
58.7


binder B


monomer B
6.9
9.47
12.13
14.7


solvent A
5
6.85
8.75
10.6


Organic
0.5
0.67
0.84
1


Additive C


Bi frit B
46.3
34.84
23.04
11.58


Ru mixture B
13.7
10.31
6.81
3.42



100
100
100
100









Results
Results are shown in Table 11.












TABLE 11







Example
Example
Example
Example



35
36
37
38




















Conductive
BiRu
BiRu
BiRu
BiRu


Paste % solids
60
45
30
15


Frit Ts (DTA)
448
448
448
448


Dried Black thickness/
4.5
3.7
3.2
2.9


um


Dried Ag/Black
13.3
12.8
12.0
12.2


thickness/um


Line resolution
70
110
110
110


4 mil line thickness/um
7.0
6.0
6.0
5.0


4 mil line edge curl/um
12.0
14.0
11.0
2.0


Peeling
Slight
high
High
none


L value Ag/Black two
17.3
20.0
29.6
44.5


layer


L value of black 1 layer
5.0
16.7
38.1
63.6


Black/Ag resistivity
9.3
6.3
5.1
6.1


mohm/sq@5 um


Black resistance (ohm)
1.2k
2.9M
>1G
>1G









As the inorganic solids content is reduced, blackness decreases and black resistance increases. At a inorganic solids content of 15 wt %, the blackness deteriorated greatly. However, at greater thickness, the inorganic solids content of 15 wt % could produce a satisfactory black color. In example 38, the BiRu pyrochlore conductive particle content was 3.42 wt %, which is on the lower edge of the conductive metal oxide particle component content range of 3-50 wt. %.
Application Examples 39-42 
The Ag conductor paste used in these examples was Ag paste C.
An investigation was made of the properties of electrodes when the inorganic solids content in the black conductive compositions was varied from 40-15 wt % and the BiRu pyrochlore content fixed at 10 wt %. Compositions are shown in Table 12.












TABLE 12







Example
Example
Example
Example



39
40
41
42




















Solids
40
30
20
15


Ingredient


Organic binder B
41.4
48.30
55.20
58.7


monomer B
10.4
12.10
13.90
14.7


solvent A
7.5
8.80
10.00
10.6


Organic
0.7
0.80
0.90
1


Additive C


Bi frit B
30
20.00
10.00
5


Ru mixture B
10
10.00
10.00
10



100
100
100
100









Results
Results are given in Table 13.












TABLE 13







Example
Example
Example
Example



39
40
41
42




















Conductive
BiRu
BiRu
BiRu
BiRu


Paste % solids
40
30
20
15


Frit Ts (DTA)
448
448
448
448


Dried Black thickness/
3.5
3.3
3.0
2.5


um


Dried Ag/Black
12.9
12.4
12.1
11.8


thickness/um


Line resolution
50
40
50
50


4 mil line thickness/um
5.8
6.0
5.8
6.0


4 mil line edge curl/um
6.8
4.5
3.0
2.5


Peeling
Slight
slight
slight
slight


L value Ag/Black two
22.6
25.0
26.9
29.0


layer


L value of black 1 layer
21.5
26.7
27.5
32.6


Black/Ag Resistivity
5.2
5.0
4.7
5.9


mohm/sq@5 um


Black resistance (ohm)
5M
1.9M
6.4M
>1 G









With conductive level at 10%, reasonable properties of the black electrode are achieved, over a range a glass content.
Application Examples 43-46 
The silver paste used in these examples was Ag paste D.
An investigation was made of the properties of electrodes when the inorganic solids content in the black conductive compositions was fixed at 26 wt % and the BiRu pyrochlore content varied from 11-14 wt %. Compositions are shown in Table 14.












TABLE 14







Example
Example
Example
Example



43
44
45
46




















% conductive
10
12
13
14


Ingredient


Organic
51
51
51
51


binder B


monomer B
12.8
12.8
12.8
12.8


solvent A
9.3
9.3
9.3
9.3


Organic
0.9
0.9
0.9
0.9


Additive C


Bi frit B
15
14
13
12


Ru mixture B
11
12
13
14



100
100
100
100









Results
Results are given in Table 15.












TABLE 15







Example
Example
Example
Example



43
44
45
46




















Conductive
BiRu
BiRu
BiRu
BiRu


% Conductive
11
12
13
14


Frit Ts (DTA)
448
448
448
448


Dried Black thickness/
3.0
3.0
3.0
3.0


um


Dried Ag/Black
12.1
12.0
12.0
12.1


thickness/um


Line resolution
80
80
80
70


4 mil line thickness/um
7.0
6.3
6.5
6.8


4 mil line edge curl/um
1.8
2.0
2.0
1.9


Peeling
none
none
none
none


L value Ag/Black two
26.7
24.3
23.3
22.7


layer


L value of black 1 layer
22.9
19.8
17.6
17.0


Black/Ag resistivity
8.5
7.7
7.5
7.9


mohm/sq@5 um


Black resistance (ohm)
150K
70K
40K
21K









In all cases, all properties were stable. At the L value of about 20, the conductive compositions for black electrodes used in the application examples appear to be practical.
Application Examples 47-50 
The Ag conductor paste used in these examples was Ag paste D.
An investigation was made of the properties of electrodes when the inorganic solids content in the black conductive compositions was fixed at 32 wt % and the BiRu pyrochlore content varied from 14-19 wt %. Compositions are shown in Table 16.












TABLE 16







Example
Example
Example
Example



47
48
49
50




















%
14
16
18
19


conductive


Ingredient


Organic
46.89
46.89
46.89
46.89


binder B


monomer B
11.78
11.78
11.78
11.78


solvent A
8.52
8.52
8.52
8.52


Organic
0.81
0.81
0.81
0.81


Additive C


Bi frit B
18
16
14
13


Ru mixture B
14
16
18
19



100
100
100
100









Results
Results are given in Table 17.












TABLE 17







Example
Example
Example
Example



47
48
49
50





















BiRu
BiRu
BiRu
BiRu


Conductive
14
16
18
19


% Conductive
448
448
448
448


Frit
3.0
3.0
3.0
3.0


Frit Ts (DTA)
12.1
12.0
12.0
12.0


Line resolution
70
70
60
70


4 mil line thickness/um
7.0
7.2
7.0
7.5


4 mil line edge curl/um
0.0
0.5
0.3
1.0


Peeling
low
low
none
none


L value Ag/Black two
21.0
20.1
19.3
18.0


layer


L value of black 1 layer
16.6
13.5
12.9
14.2


Black/Ag resistivity/
8.1
7.5
7.2
7.5


mohm/sq@5 um


Black resistance (ohm)
60K
25K
15K
10K









Within the range of inorganic solids content shown in these examples, very practical black electrodes with L value below 20 can be designed.
The above examples show that the lead-free black conductive compositions of the present invention maintain a good balance of all properties desired for black electrodes.

## Claims

1. A black conductive composition comprising, based on the total composition weight percent:
3-50 weight percent of conductive metal oxide particles selected from RuO2, ruthenium polyoxide, and mixtures thereof;
25-85 weight percent organic matter comprising organic polymer binder selected from the group consisting of copolymers and interpolymers made from (1) non-acidic comonomers selected from the group consisting of C1-10 alkyl acrylates, C1-10 alkyl methacrylates, styrene, substituted styrene, and combinations thereof, and (2) acidic comonomers and acid comonomers including an ethylenically unsaturated carboxylic acid, said organic polymer binder being at least 15 wt % of the total polymer weight; and organic solvent; and
5-70 weight percent of one or more lead-free bismuth glass binders wherein said glass binder comprises, based on weight percent total glass binder composition: 55-85% Bi2O3, 0-20% SiO2, 0-5% Al2O3, 2-20% B2O3, 0-20% ZnO, 0-15% of one or more of oxides selected from BaO, CaO, and SrO; and 0-3% of one or more of oxides selected from Na2O, K2O, Cs2O, Li2O and mixtures thereof; and
wherein the softening point of said glass binder is in the range 400-600° C.; and wherein the surface area to weight ratio of said conductive metal oxide particles are in the range of 2 to 20 m2/g; and
wherein said composition is characterized by being lead-free.

2. The black conductive composition of claim 1 wherein ruthenium polyoxide is selected from the group consisting of Bi2Ru2O7, CuxBi2-xRuO7, GdBiRu2O7, and mixtures thereof.

3. The black conductive composition of claim 1 further comprising conductive metal particles selected from gold, silver, platinum, palladium, copper and mixtures thereof.

4. The black conductive composition of claim 1 wherein said ruthenium polyoxide has a surface area per weight ratio above 5 m2/g.

5. A layer comprising the composition of claim 1 wherein said composition has been processed to remove the organic solvent.

6. A black electrode formed from the black conductive composition of any one of claims 1 and 3.

7. A single layer electrode formed from the composition of claim 3.

8. A flat panel display comprising the electrode of claim 6.

9. The black conductive composition of claim 3 wherein said conductive metal particles are spherical in shape.