CN1881482A - Black conductive thick film compositions, black electrodes, and methods of forming thereof - Google Patents
Black conductive thick film compositions, black electrodes, and methods of forming thereof Download PDFInfo
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- CN1881482A CN1881482A CN 200610082024 CN200610082024A CN1881482A CN 1881482 A CN1881482 A CN 1881482A CN 200610082024 CN200610082024 CN 200610082024 CN 200610082024 A CN200610082024 A CN 200610082024A CN 1881482 A CN1881482 A CN 1881482A
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Abstract
This invention is directed to black conductive compositions, black electrodes made from such compositions and methods of forming such electrodes.
Description
The application requires to enjoy the U.S. Provisional Application No.60/660 that submitted on March 9th, 2005, the U.S. Provisional Application No.60/690 that submit to 126 and 2005 year June 14,283 priority.
Technical field
The present invention relates to black conductive compositions, black electrode that makes by described composition and the method for making this electrode, the invention particularly relates to described composition, electrode and the manufacture method thereof used on flat-panel monitor, flat-panel monitor comprises AC plasma display (AC PDP).The invention further relates to AC PDP device itself.
Background technology
Though what discuss in the background technology of the present invention is the application of plasma display plate (PDP), generally speaking the present invention can be regarded as and is applicable to any flat panel display applications.
General PDP comprises a pair of forward and backward dielectric base, thereby their unit that has formed many as display element staggered relatively, each unit is determined by the dielectric base that is provided with constant interval, and between dielectric base, be formed with the barrier layer, unit, the inner surface of dielectric base is provided with two crossed electrodes, be provided with dielectric layer between described electrode, it can cause making in many unit and discharges when applying alternating current.Owing to fed alternating current, formed phosphor screen sends light and display image on the wall of barrier layer, unit, and they pass transparent dielectric base (being commonly referred to as front glass substrate or plate).
Show that contrast is an aspect of being concerned about during PDP makes, it has influence on the final image that the consumer sees.In order to improve the demonstration contrast, it is vital reducing the outside reflection of light that suprabasil electrode and the conductor of front glass produced in the PDP device.This reduction can become black by electrode when the display header board is seen and conductor and realize.
Furthermore, the PDP device adopts in the prior art black conductor composition and black electrode contain lead and cadmium, and its caused environmental problem is another aspect of being concerned about during PDP makes.People need reduce and/or eliminate in unlicensed tour guide's body composition and the electrode amount of plumbous and cadmium and keep composition and required physics and the electrology characteristic of electrode simultaneously.
Such as, at the flat 10[1998 of Japanese Patent Laid-Open Publication No.]-73233 with and the Japanese publication No.2004-158456 that divides an application in, the black electrode composition that can form light comprises conductive particle, this conductive particle is made up of at least a material and a kind of inorganic bond that is selected from ru oxide, ruthenium Quito oxide (ruthenium polyoxide) or its mixture, and disclose the black electrode of using above-mentioned particle, used the method for the plasma display plate and this plasma display plate of manufacturing of above-mentioned black electrode.These lists of references do not relate to unleaded unlicensed tour guide's body composition.In above-mentioned document, do not have to describe about the performance of unleaded unlicensed tour guide's body composition intensity, the balance of its electric property such as resistance and the various performances of PDP electrode such as outward appearance, roasting composition gained black electrode.
Japan Patent No.3510761 discloses that a kind of alkalescence that is applicable to plasma display plate can be developed and the conducting composition of optical hardening, by photoetching be easy to form the telegraph circuit of high precision on large tracts of land 600 ℃ of following roastings.Above-mentioned composition comprises (A) copolymer resins, and this copolymer resins is glycidyl acrylate and/or glycidyl methacrylate to be added in methyl isobutyrate and methacrylic acid and/or the acrylic acid copolymer obtain; (B) photochemical polymerization reaction initiator; (C) monomer of photopolymerizable; (D) at least a conductive metal powder that is selected from Au, Ag, Ni and Al; (E) glass dust; (F) a kind of phosphate cpd.Mentioning a kind of in this piece document especially is low-melting glass dust of main component with lead oxide preferably, does not have about the particularly description of black conductive compositions of unleaded electrically conductive composition in this piece document simultaneously.
The conducting composition that substrate is had after a kind of roasting the alkaline development of good adhesive property is disclosed among the Japan Patent No.3541125, its by the adhesion inhibition between the layer curl, thereby be easy to form by photoetching on large tracts of land the conducting channel pattern of high precision, it is particularly useful for forming the bottom electrode circuit of bus electrode in the preceding substrate of plasma display plate.Consisting of of above-mentioned composition: (A) carboxylic fat; (B) can carry out photopolymerisable monomer; (C) photochemical polymerization reaction initiator; (D) contain the synthetic no crystal silicon soil fine powder of silanol group: (E) conducting powder: (F) heat-resisting mineral black can be arranged if desired; (G) glass dust; (H) stabilizer.Mentioning a kind of in this piece document especially is low-melting glass dust of main component with lead oxide preferably, does not have the description about unleaded electrically conductive composition, particularly black conductive compositions simultaneously in this piece document.
Japan Patent No.3479463 discloses a kind of optical hardening electrically conductive composition and has used this composition to form the plasma display plate (PDP) of bottom (black layer) telegraph circuit, described composition is behind super-dry, exposure, development and calcination steps, substrate is had good adhesion property, and satisfying the dual needs of enough conductivity and blackness after dissolving and the roasting again.First of the composition basic execution mode described in this piece document comprises (A) unlicensed tour guide electricity particulate, and it has 20m
2The above specific area of/g and comprise a kind of ru oxide or other ruthenium compound of being selected from least, the material of copper-chrome black composite oxides and copper-iron black composite oxides, (B) a kind of organic binder bond, (C) a kind of photopolymerisable monomer and (D) a kind of photochemical polymerization reaction initiator of carrying out.Except said components, also comprise (E) fine inorganic particles in second execution mode.Fine inorganic particles described in this piece document in the composition (E) also can comprise the glass dust of softening point between 400-600 ℃, conductive powder, heat-resisting mineral black, Cab-O-sil or the like.Yet in the described composition of this piece document, glass dust is not a kind of necessary component, even and add glass ingredient, lead oxides also remains preferred key component, this piece document does not disclose unleaded black conductive compositions.
Japan Patent No.3538387 discloses a kind of plasma display plate (PDP) that has the optical hardening electrically conductive composition of good memory property and use this composition formation bottom (black layer) telegraph circuit, described composition is behind different dryings, exposure, development and calcination steps, substrate is had good adhesion property, and satisfying the needs of blackness after dissolving and the roasting again.The first basic execution mode of this light-curable resin composition comprises (A) cobaltosic oxide (Co
3O
4) black particle, (B) organic binder bond (C) can carry out photopolymerisable monomer and (D) photochemical polymerization reaction initiator.Except said components, also comprise (E) fine inorganic particles in second execution mode.Fine inorganic particles described in this piece document in the composition (E) comprises the glass dust of softening point between 400-600 ℃, conductive particle, heat-resisting mineral black, Cab-O-sil or the like.Yet the composition in this piece document does not comprise electric conducting material such as aluminium oxide, and glass dust neither a kind of essential composition.Even adding glass ingredient, lead oxides also remain preferred key component, this piece document does not disclose unleaded black conductive compositions.
Japan Patent No.3538408 discloses a kind of plasma display plate (PDP) that has the optical hardening electrically conductive composition of good memory property and use this composition formation bottom (black layer) telegraph circuit, described composition is behind different dryings, exposure, development and calcination steps, substrate is had good adhesion property, and satisfied the dual needs of enough conductivity and blackness after dissolving and the roasting again.The first basic execution mode of this light-curable resin composition comprises ru oxide or other ruthenium compound that (A) black inorganic fine particles applies such as inorganic bond, copper-chrome black composite oxides and copper-iron black composite oxides, cobalt/cobalt oxide etc., (B) organic binder bond, (C) can carry out photopolymerisable monomer and (D) photochemical polymerization reaction initiator.The optical hardening composition is characterised in that it comprises the black inorganic fine particles (A) that is coated with inorganic binder in this piece document.The described particulate (A) that is coated with inorganic binder obtains by the fused mass of pulverizing inorganic fine particles and inorganic binder, adopt in this piece document the inorganic binder of softening point between 400-600 ℃ and preferred be the glass dust of main component with lead oxide, unleaded black conductive compositions is not disclosed.
Summary of the invention
The invention provides the novel black conductive compositions of use in flat-panel monitor, the black electrode made from it is the performance of all preferred electrode of balance ideally, and this electrode performance comprises electrode pattern performance, blackness, resistance and storage stability.And the electrode of said composition and manufacturing thereof is not leaded.
The black conductive composition that is provided comprises (based on the percentage of total composition):
The conductive metal oxide particle of 3-50 percetage by weight is selected from RuO
2, poly oxide of ruthenium and composition thereof;
The organic substance of 25-85 percetage by weight, it comprises organic polymer binder and organic solvent;
The unleaded bismuth glass adhesive of one or more of 5-70 percetage by weight, wherein said glass glue comprises: the Bi of 55-85%
2O
3, 0-20% SiO
2, 0-5%Al
2O
3, 2-20% B
2O
3, the ZnO of 0-20%, one or more of 0-15% are selected from the oxide of BaO, CaO and SrO; Be selected from Na with one or more of 0-3%
2O, K
2O, Cs
2O, Li
2O oxide and their mixture, wherein said content is based on the percetage by weight of total glass glue composition.
The softening point of wherein said glass glue is in 400-600 ℃ of scope; And
Wherein said composition is characterised in that unleaded or unleaded substantially.
Above-mentioned composition further comprises conducting metal particles, and it is selected from gold, silver, platinum, palladium, copper and their mixture.Can handle above-mentioned composition to remove organic solvent.Invention further relates to the black electrode of above-mentioned black conductive compositions and comprises the flat-panel monitor of this electrode.
The accompanying drawing summary
Fig. 1 is the perspective view according to the amplification of the AC PDP device of one embodiment of the invention making.
Fig. 2 is the bus electrode of making on the same substrate of glass, places the interconnect electrode between the bus electrode and the method flow diagram of transparency electrode: the step that (A) applies light sensitivity thick film combination layer in order to form black electrode; (B) apply the step of light sensitivity thick film conductive composition in order to form bus electrode; (C) step of the electrode pattern of curing exposure; (D) development step; (E) calcination steps.
Fig. 3 is the bus electrode of making on the same substrate of glass, places the interconnect electrode between the bus electrode and the method flow diagram of transparency electrode: the step that (A) applies light sensitivity thick film combination layer in order to form black electrode; (B) step of the electrode pattern of curing exposure; (C) development step; (D) calcination steps; (E) apply the step of light sensitivity thick film conductive composition in order to form bus electrode; (F) by making the second bus electrode composition layer make the electrode pattern step of curing with the image format exposure; (G) development step; (H) calcination steps.
Description of reference numerals
1 transparency electrode
2 addressing electrodes
3 fluorescent materials
Barrier layer, Unit 4
5 front glass substrates
6 back substrate of glass
7 bus flow guiding electrodes
The 7a exposed portion
The 7b unexposed portion
8 dielectric layers
9 protectiveness MgO layers
10 black electrode (photosensitive thick-film electrode layer)
The 10a exposed portion
The 10b unexposed portion
The 11MgO layer
13 optical tools (target)
Detailed Description Of The Invention
An embodiment of the invention relate to black conductive compositions, it is characterized in that unleaded.During based on composition total weight %, black conductive compositions comprise 3-50wt% by RuO
2, the unleaded conducting metal oxide (oxide has metallic conductivity) made of ruthenium Quito oxide or their mixture and the unleaded bi-based glass adhesive of 5-70wt%, glass glue has following characteristics:
(I) glass ingredient
55-85wt％ Bi
2O
3，
0-20wt％ SiO
2，
0-5wt％ Al
2O
3，
2-20wt％ B
2O
3，
0-20wt％ ZnO，
One or more of 0-15% are selected from BaO, the oxide of CaO and SrO (under the situation of oxide mixture, maximum total amount is 15wt%).
One or more of 0-3% are selected from Na
2O, K
2O, Cs
2O, Li
2The oxide of O and their mixture.(under the situation of oxide mixture, maximum total amount is 3wt%)
(II) softening point: 400-600 ℃
In the present invention, ruthenium Quito oxide is preferably Bi
2Ru
2O
7, Cu
xBi
2-xRuO
7Or GdBiRu
2O
7
The present invention is the black electrode about being made by such black conductive compositions also.Have good balance in the various performances of black conductive compositions provided by the present invention, such as the caking property after the calcining, outward appearance and dimensional stability, resistance and blackness, black electrode provided by the invention also has such performance.
Unleaded or unleaded substantially black conductive compositions is characterised in that: in based on composition total weight, it comprises by RuO
2, the 3-50wt% that makes of ruthenium Quito oxide or their mixture unleaded conducting metal oxide, the unleaded bi-based glass adhesive of the organic substance of 25-85wt% and 5-70wt% with particular characteristic,
To being described below of the black conductive compositions among the present invention.
(A) conductive metal oxide particle
Black conductive compositions among the present invention comprises (a) conducting metal oxide (oxide with conductivity of metal; RuO
2And/or ruthenium Quito oxide is as conductive component).Ruthenium Quito oxide is a kind of pyrochlore oxide, and it is a kind of Ru
+ 4, Ir
+ 4Or combinations thereof the multicomponent compound, it can be by following general formula:
(M
xBi
2-x)(M’
yM”
2-y)O
7-z
In general formula, M is selected from the group of being made up of yttrium, thallium, indium, cadmium, lead, copper and rare earth material; M ' is selected from the group of being made up of platinum, titanium, chromium, rhodium and antimony; M " be ruthenium, iridium or their mixture; X is 0-2 but for monovalence copper x≤1, y is 0-0.5, is rhodium or greater than 1 platinum but work as M ', and when titanium, chromium, rhodium or antimony, y is 0-1, and z is 0-1, but when M was divalence lead or cadmium, z equaled about x/2 at least.
Above-mentioned ruthenium base pyrochlore oxide is in U.S. Pat 3,583, detailed description arranged in 931, at this with reference to quoting the document.
When to contain lead system be acceptable, containing plumbous ruthenium base pyrochlore oxide can use in the present invention.The example of such oxide comprises: Pb
2Ru
2O
6, Pb
1..5Bi
0.5Ru
2O
6.5, PbBiRu
2O
6.75
Preferred ruthenium Quito oxide is the ruthenate Bi of bismuth
2Ru
2O
7, Cu
xBi
2-xRuO
7Or GdBiRu
2O
7These materials can easily obtain with pure form, and they can not have a negative impact to glass glue, and when being heated to about 1000 ℃ in air, they are stable, even also relatively stable in reducing atmosphere.
Thick film combination among the present invention uses a kind of Bi base glass dust, is that the BiRu pyrochlore is as the conductive oxide component, because therefore the expense of the oxide component of the chemical compatibility of oxide and calcining matter and reduction is very favourable.For example, although RuO
2As a kind of unlicensed tour guide's electroxidation thing component, the Ru composition is at RuO
2In accounted for 70% greatly, so it is still very expensive.The BiRu pyrochlore contains the Ru composition and is approximately 30%, is RuO
2Half, be lower than 600 ℃ down and silver significant chemical reaction does not take place, and with except RuO
2Compare with other black pigment outside the Ru, itself and glass have good wetting property, so it is a kind of preferred unleaded unlicensed tour guide's electroxidation thing component.
The pyrochlore oxide content of ruthenium-oxide and/or ruthenium accounts for the 3-50% of composition total weight, is preferably 6-30wt%, and more preferably 8-25wt% most preferably is 9-20wt%.
The specific area scope of conducting metal oxide is at 2-20m among the present invention
2/ g.In one embodiment, scope is 5-15m
2/ g.In further execution mode, the scope of specific area is 6-10m
2/ g.
Black conductive compositions of the present invention can be used for the black electrode layers of the double-layer structure of bus electrode.Usually, a bus electrode comprises a high-conductive metal layer and a black electrode layers, and black electrode layers is as the bottom (between bus electrode and transparent substrates) of bus electrode.Composition of the present invention is suitable for such application.Black electrode layers among the present invention comprises the conducting metal oxide of the necessary component of conduct described in above-mentioned (A).Except the conducting metal oxide described in above-mentioned (A), the conducting metal particles described in (B) below black electrode layers also can optionally comprise.When the conducting metal particles that comprises in the black electrode layers described in (B), can use a kind of structure (that is, high-conductive metal layer and black electrode layers are combined into one deck) of individual layer.
(B) conducting metal particles in the black conductive compositions
As mentioned above, black composition of the present invention can optionally use noble metal, and it comprises Au, Ag, Pd, Pt and Cu and composition thereof.In fact the Any shape metal dust comprises that spherical particle and thin slice (shaft-like, taper and tabular) may be used to composition of the present invention.Preferred metal dust is selected from and comprises gold, silver, and platinum, palladium is in the group that copper and their mixture constitute.Particle is preferably spherical.Have been found that dispersion of the present invention must not contain the conducting metal solid of a large amount of particle diameters less than 0.2 μ m.If the particle of this small particle diameter exists, when its film or layer by roasting to remove organic media and to carry out organic bond and during the roasting of metal solid thing, be difficult to fully reach the organic media that burnouts fully.When this dispersion was used to make the thick film paste thing, this pastel applied by silk screen printing usually, and maximum particle diameter should not surpass the thickness of web plate.The preferred conductive solids particle diameter of 80wt% at least drops in the scope of 0.5-10 μ m.
In addition, the specific area ratio of preferred conducting metal particles is no more than 20m
2/ g preferably is no more than 10m
2/ g is more preferably no more than 5m
2/ g.When using the specific area ratio greater than 20m
2During the metallic particles of/g, the roasting characteristic of simultaneous inorganic bond is had a negative impact.Be difficult to reach fully and burnout, and bubble occurs.
Although dispensable, often add cupric oxide and adhere to improve.Cupric oxide should exist with the form of crushed fine particle, the about 0.1-5 micrometer range of preferred size.When as Cu
2When O exists, cupric oxide account for composition total weight about 0.1% to about 3%, preferably about 0.1-1.0%.Part or all of Cu
2O can be replaced by the CuO of equimolar amounts.
And, in composition of the present invention, can optionally add non-conducting material in the black conductive compositions under the necessary situation.Preferred non-conducting material can be inorganic black pigment, and this black pigment can obtain in commerce easily.Among the present invention, the form of non-conducting material is unimportant.When utilizing silk screen printing that powder is carried out dispersion treatment, the largest particles diameter of powder can not surpass the thickness of silk screen.
(C), glass glue (glass dust)
Employed glass glue (glass dust) has promoted the roasting of conductive component particle among the present invention.Glass glue used in the present invention is unleaded, low-melting adhesive.
Glass glue is the bismuthino amorphous glass of lead-free and cadmium-free.Other Unlead low-smelting point glass is P base or Zn-B based composition and use thereof in packaging.Yet P base glass does not have excellent waterproofness, and Zn-B glass is difficult to obtain amorphous state, so Bi base glass is preferred.Bi base glass can be made relative low-melting glass, and does not need to add alkali metal, and is processed into powder easily.Among the present invention, the Bi glass with following feature is most preferred.
(I) glass ingredient
55-85wt％ Bi
2O
3：
0-20wt％ SiO
2
0-5wt％ Al
2O
3
2-20wt％ B
2O
3：
0-20wt％ ZnO
One or more are selected from BaO 0-15wt%, the oxide of CaO and SrO (under the situation of oxide mixture, maximum total amount is 15wt%).
One or more of 0-3wt% are selected from Na
2O, K
2O, Cs
2O, Li
2The oxide of O and their mixture.(under the situation of oxide mixture, maximum total amount is 3wt%).
(II) softening point: 400-600 ℃
In this manual, " softening point " means the softening point that differential thermal analysis (DTA) is measured.
Among the present invention, for all properties of the black electrode guaranteeing to obtain has good balance, glassy bond component and softening point are very important.
When softening point was lower than 400 ℃, glass can melt, and organic material can be decomposed, thereby caused bubble can occurring in the composition.Therefore the softening point of glass is preferably greater than 400 ℃.On the other hand, in necessary enough the softening of the sintering temperature lower-glass that provides.For example, when the sintering temperature that uses was 550 ℃, softening point should be less than 520 ℃, if softening point surpasses 520 ℃, the stripping layer appears in place, electrode angle, and performance is affected such as resistance etc., and this has damaged the balance of electrode performance.If use high sintering temperature (this depends on substrate), can both be used up to the glass of 600 ℃ of softening points.
Glass glue among the present invention preferably has the D of the 0.1-10 μ m of Microtrac measurement
50(that is, the size of this half particle of some place is less than particular value, and the size of half particle is greater than this particular value).Preferred, glass glue has the D of 0.5-1 μ m
50In desirable industrial technology, by mixing and dissolving, be quenched to cullet such as raw material such as oxide, hydroxide, carbide, mechanical crushing (wet method, dry method), dry under the broken situation of wet-milling then, make glass dust thus.Afterwards, necessary, classify according to required size.It is desirable to, the average grain diameter of the glass glue among the present invention is less than the thickness that will form black conductive layer.
Also can use the mixture of glass among the present invention with different softening point.The glass of high softening-point can combine with the glass of low softening point.The ratio of different softening point glass is decided by the accurate balance of the electrode performance of needs.Can comprise in some glass glue that softening point is higher than 600 ℃ glass.
Based on composition total weight, the glass glue component should be 5-70wt%.When the bonding glass agent content too hour, with being connected of substrate be faint.
Composition of the present invention also can comprise organic substance.Organic substance in the composition accounts in the 25-85wt% scope of composition gross weight.Organic substance contained among the present invention can comprise organic bond and organic solvent.Organic substance may further include light trigger, optical hardening monomer or the like.These are explained below.
(D) organic polymer binder
Polymer adhesive is important for composition of the present invention, and their selection must be considered water base development property and high dissolubility again.Following adhesive can satisfy these requirements.These adhesives are by the copolymer of following compound or mutual aggressiveness: (1) nonacid comonomer, and such as acrylic acid C
1-10Arrcostab, methacrylic acid C
1-10The styrene of Arrcostab, styrene, replacement or its mixture; (2) contain the arcylic acid monomer of vinyl unsaturated carboxylic acid, it is the 15wt% of total polymer weight at least.
Arcylic acid is important with the existence of monomer for this technology in the composition.When utilizing this acidic functionality, it is feasible developing at alkaline aqueous solution, such as the aqueous solution of 0.4% sodium carbonate.When arcylic acid with monomer when existing less than 15% concentration, can not wash said composition fully off with moisture alkali.When arcylic acid with monomer when existing greater than 30% concentration, under development conditions, the said composition less stable, part is developed and is occurred in image section.Suitable arcylic acid comprises that with monomer the vinyl unsaturated monocarboxylic acid is such as acrylic acid, methacrylic acid or crotonic acid etc.; The vinyl unsaturated dicarboxylic acid is such as fumaric acid, itaconic acid, citraconic acid, vinyl butanedioic acid and maleic acid etc. and their half ester, and in some cases, can be their acid anhydride and their mixture.For roasting cleanly in hypoxic atmosphere, preferable methyl acrylic copolymer but not acrylic copolymer.
When nonacid comonomer was aforesaid alkyl acrylate or alkyl methacrylate, preferably these nonacid comonomers accounted for the 50wt% at least of polymer adhesive, preferred 70-75wt%.When nonacid comonomer was the styrene of styrene or replacement, preferably these nonacid comonomers accounted for the 50wt% of polymer adhesive, and in addition 50wt% be acid anhydrides, such as the half ester of maleic anhydride.The preferred styrene that replaces is AMS.
Although be not preferred, but the nonacid part of polymer adhesive can contain other the nonacid comonomer less than about 50wt%, the styrene part of the alkyl acrylate of thing replace polymeric, alkyl methacrylate, styrene or replacement as an alternative.For example they comprise: acrylonitrile, vinyl acetate, acrylamide.Yet, since the difficult after-flame fully of these compounds, preferred this class monomer that uses less than about 25wt% of polymer adhesive total weight.Also the mixture that can use single copolymer or copolymer is as adhesive, as long as each in these satisfies above-mentioned various standard.Except that above-mentioned copolymer, other example comprises polyolefin such as polyethylene, polypropylene, polybutene, polyisobutene and ethylene-propylene copolymer etc., can also be polyethers, such as the low alkylene oxide polymer that comprises poly(ethylene oxide).
By normally used solution polymerization technique well known by persons skilled in the art, produce polymer with the acrylic ester polymerization method.
Usually, by in organic solvent with low relatively boiling point (75-150 ℃), with α-or β-vinyl unsaturated acids (arcylic acid monomer) but mix with the vinyl monomer (nonacid comonomer) of one or more copolymerization, to obtain 10-60% monomer mixture solution, then by in monomer, adding polymerization catalyst, then carry out polymerization, heating obtains mixture under the reflux temperature of normal pressure and solvent.After polymerization reaction was finished basically, prepared acidic polymer solution was cooled to room temperature.Collect sample, measure polymer viscosity, molecular weight and acid equivalent.
The above-mentioned molecular weight that contains the acid polymer adhesive should be lower than 50,000.
When above-mentioned composition applies by silk screen printing, the Tg of polymer adhesive (vitrification point) should be above 60 ℃.
Organic polymer binder generally accounts for the 5-45wt% of dry photopolymerization layer gross weight.
(E) light trigger
To be those be exposed under 185 ℃ or lower temperature the light trigger that is fit in the actinic radiation for inertia but produce the light trigger of free radical.These light triggers are the compounds that have 2 intermolecular rings in the conjugation carbocyclic ring system, and they comprise multinuclear quinone replacement or unsubstituted, for example 9, the 10-anthrone, 2-methylanthraquinone, the 2-EAQ, 2-tert-butyl group anthrone, the prestox anthraquinone, 1, the 4-naphthoquinones, 9, the 10-phenanthrenequione, benzanthracene-7, the 12-diketone, 2,3-aphthacene-5,12-diketone, the 2-methyl isophthalic acid, the 4-naphthoquinones, 1,4-dimethyl anthraquinone, 2,3-dimethyl anthraquinone, 2-phenyl anthraquinone, 2,3-diphenyl anthraquinone, the retene quinone, 7,8,9,10-tetrahydro aphthacene-5,12-diketone and 1,2,3,4-tetrahydro benzo anthracene-7,12-diketone.Other useful light trigger is in U.S. Pat 2,760, has in 863 to state that [more wherein said light triggers are thermoactive, such as connecting ketaldonyl alcohol, for example acetophenone or new penta acyloin (Pivaloin) under 85 ℃ low temperature; Acyloin ether, for example acetophenone methyl or ethylether; Alpha-Methyl acetophenone, α-allyl benzene ethyl ketone, α-phenyl acetophenone, thioxanthones and their derivative, hydrogen donor, the fragrant acyloin that hydrocarbon replaces etc.].
Concerning initator, can use photo-reduction dyestuff and reducing agent.These are in U.S. Pat 2,850,445,2,875,047,3,097,096,3,074,974,3,097,097 and 3,145,104 have description, and they comprise azophenlyene, oxazine and quinone, Michler's keton for example, ethyl Michler's keton, benzophenone and comprise leuco dye 2,4,5-triphenyl imidazole radicals dimer and their mixture (are documented in U.S. Pat 3,427,161,3 at interior hydrogen donor, 479,185 and 3,549,367).In addition, U.S. Pat 4,162,162 sensitizers of introducing can use with light trigger and light inhibitor.The amount of light trigger or photoinitiator system is the 0.05-10wt% of the photopolymerization layer total weight of drying.
(F) monomer of optical hardening
The monomer component of optical hardening of the present invention has at least a polymerisable vinyl group, but and contains the vinyl unsaturated compound of at least one addition polymerization.
This compounds is by the formation of free radical polymerization thing, and carries out the addition polymerization of chain growth.This monomeric compound is an on-gaseous, and promptly boiling point is greater than 100 ℃ and organic polymer binder had plasticization.
Preferably can use separately or mix the monomer that uses and comprise acrylic acid tertiary butyl ester and methacrylic acid tertiary butyl ester with other monomer, 1,5-pentanediol diacrylate and 1,5-pentanediol dimethylacrylate, acrylic acid N, N-dimethylamino ethyl ester and methacrylic acid N, the N-dimethylamino ethyl ester, glycol diacrylate and ethylene glycol dimethacrylate, 1,4-butanediol diacrylate and 1, the 4-butanediol dimethylacrylate, diethylene glycol diacrylate and diethylene glycol dimethacrylate, 1,6-hexanediyl ester and 1, the 6-hexanediol dimethacrylate, 1, ammediol diacrylate and 1, the ammediol dimethylacrylate, 1,10-decanediol diacrylate and 1,10 decanediol dimethylacrylates, 1,4-cyclohexanediol diacrylate and 1,4-cyclohexanediol dimethylacrylate, 2,2-dihydroxy methylpropane diacrylate and 2,2-dihydroxy methylpropane dimethylacrylate, glycerine diacrylate and glycerine dimethylacrylate, tripropylene glycol diacrylate and tripropylene glycol dimethylacrylate, glycerol tri-acrylate and glycerine trimethyl acrylic ester, trimethylolpropane triacrylate and trimethylol-propane trimethacrylate, with class with those in U.S. Pat 3,380, the compound of introducing in 381, such as 2,2-two (to hydroxyphenyl)-propane diacrylate and 2,2-two (to hydroxyphenyl)-propane dimethylacrylate, tetramethylol methane tetraacrylate and pentaerythrite tetramethyl acrylate, triethylene glycol diacrylate, polyoxy ethyl-1,2-two-(to ethoxy) propane dimethylacrylate, bisphenol-A two-(3-methacryloxy-2-hydroxypropyl) ether, bisphenol-A two (3-acryloxy-2-hydroxypropyl) ether, bisphenol-A two (2-methylacryoyloxyethyl) ether, bisphenol-A two (2-acrylyl oxy-ethyl) ether, 1,4-butanediol two-(3-methacryloxy-2-hydroxypropyl) ether, the triethylene glycol dimethylacrylate, polyoxyethyl propyl trimethylolpropane triacrylate, butanediol diacrylate and butanediol dimethylacrylate, 1,2,4-butanediol triacrylate and 1,2,4-butanediol trimethyl acrylic ester, 2,2,4-trimethyl 1,3-pentanediol diacrylate and 2,2,4-trimethyl-1,3-pentanediol dimethylacrylate, 1-styrene-1, the 2-dimethylacrylate, diallyl fumarate, styrene, 1,4-Benzenediol dimethylacrylate, 1,4-di isopropenylbenzene and 1,3,5-three isopropenylbenzenes.
It is useful that molecular weight is lower than 300 vinyl unsaturated compound, and for example aklylene glycol diacrylate or PAG diacrylate and those are in U.S. Pat 2,927, but the compound of the ethene end key of introducing in 022 that contains addition polymerization.Aklylene glycol diacrylate or PAG diacrylate for example have the C of 1-10 ehter bond by aklylene glycol or PAG preparation
2-15Aklylene glycol.
Other useful monomer is at U.S. Pat .5, and is open in 032,490.
Preferred monomer is the trimethylolpropane triacrylate and the trimethylolpropane methacrylate of polyoxyethyleneization, the pentaerythritol triacrylate of vinylation, trimethylolpropane triacrylate and trimethylolpropane methacrylate, dipentaerythritol-hydroxyl five acrylate and 1,10-decanediol dimethylacrylate.
Other preferred monomer is the poly-acetate lactone-mono acrylic ester of monohydroxy, polyethyleneglycol diacrylate (molecular weight about 200), polyethylene glycol dimethacrylate (molecular weight about 400).Based on the total weight of the photopolymerizable layer of drying, the amount of unsaturated monomer component is 1-20wt%.
(G) organic media
Organic media is mainly used in the dispersion thing easily is coated in pottery or other substrate, and wherein said dispersion thing contains the composition that fine gtinding is crossed.Therefore, at first organic media should be able to be with stable manner dispersing solid composition; The second, the rheological behavior of organic media must give dispersion good coating characteristic.
In organic media, can be that the solvent composition of solvent mixture should be selected from those solvents of dissolve polymer and other organic component fully.This solvent should be (non-reacted) of inertia for other composition of paste composition.This solvent should have sufficiently high volatility, even thereby under atmospheric pressure and relative low temperature, apply, this solvent also can evaporate from disperse thing, but, the volatility of this solvent should be too not high, otherwise in silk-screen printing technique, can make pastel rapid draing on web plate at room temperature.Be used for boiling point that the preferred solvent of paste composition should have under atmospheric pressure less than 300 ℃, preferably less than 250 ℃.Such solvent comprises aliphatic alcohol or their ester, for example acetic acid esters or propionic ester; Terpenes is pine-seed oil and α-or β-terpineol or its mixture for example; Ethylene glycol, ethylene glycol-monobutyl ether and glycol ester be butyl cellosolve acetate for example; Butyl carbitol and carbitol ester, for example acetate of butyl carbitol and carbitol acetic acid esters, Texanol (2,2,4-trimethyl 1,3-pentanediol-isobutyrate and other appropriate solvent.
Except above-mentioned component, composition of the present invention also can comprise other component as described below.
(H) other component
Other component well known in the art comprises dispersant, stabilizer, plasticizer, release agent, stripping agent, anti-foaming agent and wetting agent.United States Patent (USP) U.S.5, the common used material of introducing in 032,490, the present invention is incorporated herein by reference.
Purposes
Composition among the present invention can combine with aforesaid light-sensitive material and constitute photosensitive composition.This photosensitive composition can use in multiple application, comprises flat panel display applications.
For example, by common pattern formation technology such as silk screen printing, chemical etching or paint-on technique such as spin coating, immersion coating, unlicensed tour guide's electric light sensitive composition can be formed film.
By using the photosensitive polymerization layer, black conductive compositions of the present invention also can be used to constitute the thick film pattern of conducting function.For example, in the patent application WO02/03766 of Keusseyan A2, description is arranged, be hereby incorporated by.Keusseyan has described the process that forms the pattern with conducting function in substrate, comprises step: (a) provide the photosensitive layer with tacky surfaces in substrate; (b) provide transfer film, it comprises movably support and at least one bed thickness film composition; (c) make photosensitive tacky surfaces exposure with image mode, thereby form imaging layer, it has the adhesive region of non-exposure and the non-adhesive region of exposure; (d) thick film combination on the transfer film is put on the imaging layer; (e) with transfer film from substrate separately, thick film is stayed the non-adhesive region of the exposure of support basically here, thereby has formed the thick film combination of patterning; (f) with the thick film combination heating of patterning, have the article of pattern with formation.
When the black conductive compositions among the present invention when the electric conducting material, these compositions can moulding in different substrates, substrate comprises insulating barrier or substrate of glass (as the bare glass plate).
Composition of the present invention can form pattern on transparent substrates, be light-sensitive material above, and it for example is exposed under the UV from transparent substrates (back side), thereby forms photomask.
Flat panel display applications
The present invention includes the black electrode that forms by above-mentioned black conductive compositions.Black electrode of the present invention can effectively be used on flat panel display is used, and particularly is applied in the AC plasma display board device.Between device substrate and conductive electrode array, form black electrode.
In one embodiment, the electrode among the present invention as described below is used in the AC PDP application.Should be understood that composition of the present invention and electrode also can be used in other flat panel display applications, and the application in AC PDP device is described and not to be thought its purposes is limited.The embodiment that black electrode of the present invention is used in the AC plasma display flat board is as described below.This moment, it comprised two-layer electrode, and described electrode is included in the black electrode between substrate and the conductive electrode (bus electrode).And, provided the method for making the AC plasma display flat board.
The AC plasma display board device is made up of the front and rear dielectric base and the electrod-array that are provided with at certain intervals, and electrod-array comprises the first and second parallel electrode complex group that are in region of discharge, and region of discharge is full of ionized gas.Upright the facing mutually of the first and second electrode complex group, region of discharge is situated between.Certain electrode pattern the insulation substrate on form, with insulator-coating on the electrod-array of at least one side of dielectric base.In this device, the electrode complex group on the anterior at least dielectric base has been equipped with the conductive electrode array group, and the conductive electrode array group is connected to same suprabasil bus electrode, and the black electrode among the present invention is formed between above-mentioned substrate and the above-mentioned conductive electrode array.
Fig. 1 is presented at the black electrode among the present invention among the AC PDP.Fig. 1 illustrates the AC PDP that uses black electrode of the present invention.As shown in Figure 1, AC PDP device has with lower member: bottom transparency electrode (1) is formed on the substrate of glass (5); Black electrode (10) is formed on transparency electrode (1) and goes up (black conductive compositions among the present invention is made black electrode (10)); Bus electrode (7) is formed on black electrode (10) and goes up (bus electrode (7) is a photosensitive conducting composition, and the conducting metal particles that it comprises is selected from Au, Ag, Pd, Pt and Cu or its mixture (this explains below in detail)).Black electrode (10) and bus electrode (7) are exposed under the light radiation with image mode and have formed pattern, in alkaline aqueous solution, develop, and under soaking condition roasting to remove organic principle and roasting inorganic material.Make black electrode (10) and bus electrode (7) patterning with same or closely similar image.Final result is that the high conductive electrode composition of roasting is shown as black on the surface of transparency electrode (1), and when being placed in the front glass substrate, outside reflection of light is suppressed.
Term " is deceived " and is meant with respect to white background, demonstrates the black color of observable remarkable contrast as used herein.Therefore, term need not be restricted to does not have the black of color.The degree of " blackness " is measured the L-value by colorimeter and is determined.The L-value is represented brightness, and wherein 100 is pure white, and the 0th, black.Though Fig. 1 shows transparency electrode, for forming plasma display device of the present invention, transparency electrode is dispensable.
When using transparency electrode, by chemical vapour deposition (CVD) or electro-deposition, spray or ion plating such as ion, with SnO
2Or ITO makes transparency electrode (1).The composition of transparency electrode and its formation method are traditional ACPDP field production technologies, are known to those skilled in the art.
As shown in Figure 1, AC PDP device of the present invention takes shape on the substrate of glass, on the metal layer of this glass patternization and roasting, has insulating barrier (8) and MgO layer (11).
The width of lead is consistent and do not have the hole or fracture, and has high conductivity, transparency between translucidus and line.
Next, described a kind of method of making bus electrode and black electrode, this electrode is positioned on the optional transparency electrode on the substrate of glass of PDP device header board.
As shown in Figure 2, the manufacture method in one embodiment of the present invention comprises series of steps ((A)-(E)).
(A) go up the photosensitive thick-film combination layer (10) that applies the formation black electrode in transparency electrode (1), described transparency electrode is used SnO by conventional method of the prior art
2Or ITO is formed on the substrate of glass (5), then dry thick film combination layer (10) under nitrogen or air atmosphere.Black electrode composition is the unleaded black conductive compositions among the present invention.(Fig. 2 (A))
(B) go up coating photosensitive thick-film electrically conductive composition (7) to form bus electrode at the first black electrode combination layer (10) of above-mentioned coating, then dry thick film combination layer (7) under nitrogen or air atmosphere.Described photosensitive thick-film electrically conductive composition composition is as described below.(Fig. 2 (B))
(C) by a smooth instrument or target (13), the first black electrode composition layer (10) of coating and the second bus electrode composition layer (7) are exposed in the actinic radiation with imaging mode (generally use the UV source), the shape of this target (13) adapts with the black electrode that is provided with corresponding to transparency electrode (1) and the pattern form of bus electrode, after developing, the conditions of exposure that uses can produce correct electrode pattern (Fig. 2 (C))
(D) with the exposed portion of the first black conductive compositions layer (10) and the second bus electrode composition layer (7) (10a, the technology of 7a) place alkaline aqueous solution, developing such as sodium carbonate or other alkaline aqueous solution of 0.4wt%.This technology has been removed the unexposed portion of layer on (10,7), and (10b 7b), and has stayed exposed portion (10a, 7a) (Fig. 2 (D)).Follow the dry development product.
(E) according to substrate material, with the product that obtains after the step (D) 450-650 ℃ of following roasting with roasting inorganic bond and conductive component (Fig. 2 (E)).
In Fig. 3, will the manufacturing process of second execution mode of the present invention be described.For convenience of description, in the same composition described in Fig. 3, use the Reference numeral identical with Fig. 2.The method of second execution mode comprises the following steps (A '-H ').
A '. go up the photosensitive thick-film combination layer (10) that applies the formation black electrode in transparency electrode (1), described transparency electrode is used SnO by conventional method of the prior art
2Or ITO is formed on the substrate of glass (5), then dry thick film combination layer (10) under nitrogen or air atmosphere.Black electrode composition is the unleaded black conductive compositions among the present invention.(Fig. 3 (A))
B '. by a smooth instrument or target (13), the first black electrode composition layer (10) of coating is exposed in the actinic radiation with imaging mode (mainly uses the UV source), the shape of this target (13) adapts with the pattern form of the black electrode that is provided with corresponding to transparency electrode (1), after developing, the conditions of exposure that uses can produce correct electrode pattern (Fig. 3 (B))
C '. in alkaline aqueous solution, with exposed portion (10a) development of the first black conductive compositions layer (10), to remove the unexposed portion (10b) (Fig. 3 (C)) of layer (10), alkaline aqueous solution is sodium carbonate or other alkaline aqueous solution of 0.4wt%.Follow the product of dry development.
D '. according to substrate material, with the product that obtains after the step (C ') 450-650 ℃ of following roasting, with roasting inorganic bond and conductive component (Fig. 3 (D)).
E ' goes up coating photosensitive thick-film electrically conductive composition layer (7) to form bus electrode in black electrode (10a), then under nitrogen or air atmosphere dry (Fig. 3 (E)) according to the roasting of the first photosensitive thick-film composition layer (10) and the part (10a) of patterning.Described photosensitive thick-film electrically conductive composition composition is as described below.
F '. by a smooth instrument or target (13), the second bus electrode composition layer (7) of coating is exposed in the actinic radiation with imaging mode (mainly uses the UV source), the shape of this target (13) adapts with pattern form corresponding to the bus electrode of transparency electrode (1) and black electrode (10a) setting, after developing, the conditions of exposure that uses can produce correct electrode pattern (Fig. 3 (F))
G '. the exposed portion (7a) with the second bus electrically conductive composition layer (7) in alkaline aqueous solution develops, and to remove the unexposed portion (7b) (Fig. 3 (G)) of layer (7), alkaline aqueous solution is sodium carbonate or other alkaline aqueous solution of 0.4wt%.Follow the dry development product.
H '. according to substrate material, with the product that obtains after the step (G ') 450-650 ℃ of following roasting, with roasting knot inorganic bond and conductive component (Fig. 3 (H)).
The 3rd execution mode (not having diagram) comprises the following (series of steps of (i)-(v)).This execution mode is particularly useful to the formation of single-layer electrodes.
I) coat black electrode composition on substrate, described black electrode composition is as the foregoing black conductive compositions of the present invention.
(ii) in substrate, coat photosensitive conducting composition.Described photosensitive conducting composition as described later.
Black composition and electrically conductive composition are exposed in the actinic radiation, to determine electrode pattern with imaging mode.
Black composition that (iv) will expose in alkaline aqueous solution and electrically conductive composition develop, to remove the part that is not exposed to actinic radiation in the composition.
(the v) electrically conductive composition that develops of roasting.
The front glass substrate assembly that forms according to said process can be used on the AC PDP.For example, with reference to figure 1, after having formed transparency electrode (1) and associated black electrode (10) and bus electrode (7) in the front glass substrate (5), apply dielectric layer (8) and MgO layer (11) on the front glass base assembly successively.Then front glass substrate (5) is connected with back substrate of glass (6).The many display units that are coated with fluorescent material and are formed with barrier layer, unit (4) by silk screen printing are set on the back substrate of glass (6).The electrode that forms in the front glass substrate is perpendicular to the addressing electrode that forms on the substrate of glass of back.The discharge space that forms between front glass substrate (5) and back substrate of glass (6) adopts glass-dead seal to seal, and simultaneously the discharge gas mixture is enclosed in this space.So just be assembled into AC PDP device.
Next, the composition of the bus electrically conductive composition that forms bus electrode is described.
The bus electrically conductive composition that is suitable among the present invention can be can the commercial photosensitive thick-film electrically conductive composition of buying.As previously mentioned, the bus electrically conductive composition comprises the conducting metal particles of (a) at least a Au of being selected from, Ag, Pd, Pt and Cu and composition thereof; (b) at least a inorganic binder; (c) light trigger; (d) optical hardening monomer.In an embodiment of the invention, the bus electrically conductive composition comprises Ag.
Conductive phase is the main component in the above-mentioned composition, and it can comprise that generally particle size range is arbitrary shape or the laminar silver-colored particle of 0.05-20 μ m (micron).Comprise silver-colored particle with reference to the described bus electrically conductive composition of an execution mode, but be not limited to this.When said composition was used in combination with the UV polymeric medium, silver granuel footpath scope was preferably 0.3-10 μ m.Preferred composition contains the silver-colored particle of the 65-75wt% that accounts for thick film paste thing total weight.
Except silver, the silver-colored electrically conductive composition that forms bus electrode can contain under the glass binder of 0-10wt% and/or the necessary situation and contain 0-10wt% refractory material or its precursor, and this refractory material can not form glass.The example of glass binder comprises the crown glass binding agent described in claims of the present invention.The refractory material and the precursor thereof that do not form glass comprise aluminium oxide, cupric oxide, gadolinium oxide, tantalum oxide, niobium oxide, titanium oxide, zirconia, cobalt/iron/chromated oxide, aluminium, copper and various can the commercial inorganic pigment of buying or the like.
Except that above-mentioned main component, add second, the 3rd or the purpose of more inorganic additives be in order to control the shape of figure, sintering degree when reduction or increase roasting keeps cementability, the decentralization of control major metal composition, stop near the variable color of bus electrode, controlling resistance, the control thermal coefficient of expansion keeps mechanical strength or the like.The selection of its type or quantity can be carried out in the scope that above-mentioned performance is not produced obvious counter productive as required.
In addition, the silver conductor composition can further contain the photosensitive medium of 10-30wt%, and wherein above-mentioned granular materials is disperseed by described medium.The example of this photosensitive medium is polymethyl methacrylate and polyfunctional monomer solution.Monomer should have low volatility, so that in the printing/drying steps process before the preparation of silver conductor composition pasty state thing and UV sclerosis, the evaporation of monomer is reduced to minimum.Photosensitive medium also contains solvent and UV initator.Preferred UV polymeric medium comprises the polymer based on methyl methacrylate/ethyl acrylate, and the ratio of said two devices is 95/5 (weight).The viscosity of above-mentioned silver conductor composition is 10-200 Pascal-second, thereby has formed free-pouring pastel.
The dielectric solvent that is fit to includes but not limited to acetate of butyl carbitol, Texanol and β-terpineol.In addition, spendable other medium comprises the organic media that aforementioned (G) part is listed, and can utilize dispersant, stabilizer etc. to handle this medium.
The photosensitive paste for preparing wettable development
(A) preparation organic material
Mixed solvent and acrylate copolymer stir, and are heated to 100 ℃ and dissolve fully up to polymer adhesive.Then the solution that obtains is cooled to 80 ℃, adds remaining organic component, stir this mixture and dissolve fully, this solution is also cooled off by 325 purpose filter screens until all solids.
(B) preparation pastel
Under gold-tinted, prepare pastel by in mixer, mixing organic media, one or more monomers and other organic component.In mixture of organic components, add inorganic material then.It is moistening by organic material until inorganic powder to mix total composition then.Use the three-roll grinder milled mixtures then.With the direct use of the pastel that obtains or by using behind 635 mesh sieves.Pastel viscosity herein can be with suitable medium or solvent adjustment to reach the viscosity that helps processing most.
In preparation paste composition and assembly, to note avoiding the pollution of impurity, because this pollution can cause defective.
(C) preparation condition
(1) formation of black electrode
Ideal thickness according to after composition and the oven dry is coated in thickener on the substrate of glass by screen printing, uses 200-400 purpose mesh screen this moment.Use 350 purpose mesh screens on substrate of glass, to apply black material among the embodiment.On the substrate of glass that forms transparency electrode (ITO film), prepare double-layer structure, with it as part of detecting.Do not prepare individual layer (black electrode layers) in the substrate of ITO film glass forming, with it as part of detecting.Part of detecting under 80 ℃ in the hot air circulate stove dry 20min, be the black electrode of 2-6 μ m to form build.
Then, the part of detecting of roasting single layer structure (having only black electrode) (referring to technology 5).
Then, handle the part of detecting (referring to technology 2-5) of double-layer structure as described below.
(2) formation of conductive bus electrode
Then, use 325 order stainless steel mesh screens, be coated with up by the silver conductor pastel of silk screen printing with Photoimageable.The silver conductor of Photoimageable is stuck with paste and is contained the bismuth-containing glass powder B of 2wt% and the silver powder of 64-72wt% (particle mean size: photosensitive silver paste 1.3-2.0 μ m).In the following embodiments, used four kinds of silver-colored conducting pastes (silver-colored thickener A, B, C, D), describe its concrete composition in the back.These four kinds of conducting pastes bring the same basically performance to bus electrode.
This part is dry again 20min under 80 ℃.The thickness of baked film is 6-10 μ m.The gross thickness of the dry film of double-layer structure is 10-16 μ m like this.
(3) UV pattern exposure
The parts of double-layer structure are exposed to the parallel UV light source of optical tool, and illumination is 5-20mW/cm
2Exposure energy: 400mJ/cm
2The noncontact exposure, mask-coating slit: 150 μ m.
(4) develop
The parts of having finished exposure place on the conveyer, then send to and spray the developer that contains the 0.4wt% aqueous sodium carbonate.The temperature of developing solution is 30 ℃, sprays under 10-20psi.The developing time of parts is 20 seconds (being equivalent to 3-4 scavenging period TTC doubly).Then adopt forced draft to blow the parts that the redundant moisture drying has been developed off.
(5) roasting
Dried parts use through furnace to carry out dry 2.5hr under air atmosphere, reach 550 ℃ up to peak temperature.
Embodiment
Among the described below embodiment, constituent content is represented with wt%.
Test process
The black film thickness of doing
Use the contact surface photometer, measure the build of black electrode as Tencor Alpha Step 2000 at four difference places of black electrode.
The Ag/ black film thickness of doing
Silver electrode is coated on the dry film of black electrode, dry then.Use the same method of said determination black electrode to measure the build that Ag/ deceives composition layer.
Linear resolution
With minimum magnification ratio is that the zoom microscope of 10 times on 20 times of eyepieces is observed ready sample.One group of best lines, just fully without any disconnection (connection between the line) or the lines of opening (lines split fully) as being used for that group of specimen linear resolution.
4 Mil wire thickness
Film thickness after the wide line place of 4 mils measures roasting is used for measuring resistivity.Use the contact surface photometer to test.
4 Mil wire edge curl
After 4 Mil wire line film thickness determination, the unusual angular protrusions of observing the edge in some cases, the length of the projection of this unusual horn shape is called edge curl.Edge curl is big more, and by printing, lamination or apply after transparent insulation material is made in roasting then, effectively film thickness will be reduced; This will cause bubble, cause the possibility of insulation breakdown, so edge curl should be avoided.Non-flanged is curled, and promptly curl is that 0 μ m expects to obtain most.Even use best leaded electrically conductive composition, edge curl approximately is 1-3 μ m.
Peel off
Observe the corner of the pattern after the roasting by microscope and peel off, it is divided into nothing, slight (or low), medium, middle height and high degree.Use best leaded electrically conductive composition at present, observed corner degree of peeling off rank is slight, and no corner is peeled off and expected most to obtain.
The L value of Ag/ black film bilayer
After the roasting, the mensuration of machinery is from the observed blackness in the back of substrate of glass.Concerning blackness, use the ∑ 80 colour measurement system measurement color (L of optical pickocff SZ and Nippon Denshoku Kogyo
*), use standard white plate to calibrate, the 0th, black, and 100 be pure white.Optionally, use Minolta CR-300 chromascope to measure color, multiple standards (white, red and black) is used in calibration.At CIE L
*a
*Measure color among the b.L
*Represent brightness, the 100th, pure white, and 0 be black.
The L value of individual layer (having only black electrode)
The insulating glass substrate of no ITO film is coated with the black electrode of above-mentioned steps (1) and is dried.Omit step (2) (3) (4), the dried black electrode that obtains roasting under the same condition of step (5) forms the black electrode individual layer of solid roasting.After the roasting, use Nippon Denshoku or Minolta CR-300 chromascope to measure color, condition determination is identical with above-mentioned double-deck L pH-value determination pH, and the 100th, pure white, and 0 be black.
Black film resistance (ohm)
Measuring the resistance of black electrode estimates.Use this method that the electric conductivity of the black layer of roasting is determined.Use above-described part of detecting (the L value of individual layer), use to have the resistance that probe distance is approximately the resistance instrument mensuration black electrode roasting film of 4cm.The resistance of the maximum that this device can be measured is 1G Ω.
The double-deck resistance (m Ω/sq@5 μ m) of black film/Ag
The sheet resistance value that double-deck resistance value is per unit roasting film thickness (5 μ m) (m Ω/sq).Measure at 4 Mil wire places.This value equals 2 times so-called than resistance (μ Ω-cm).When using leaded electrically conductive composition of the prior art (article number of plumbous type is the paste of DC243, obtains from E.I.du Pont de Nemoursand Company) and Ag electrode, known value approximately is 11-13m Ω/sq@5 μ m.This value is low more good more.
Nomenclature
Ts: the softening point that differential thermal analysis (DTA) obtains.
Given below is each component among the specification embodiment.
Organic component
Organic bond A
Monomer A: monomer TMPEOTA (trihydroxy methyl propyl group ethyoxyl triacrylate)
Solvent orange 2 A: solvent, Texanol
Organic additive A: additive, malonic acid
Organic additive B: additive B HT
Organic bond B
Monomers B: oligomer, CN2271, the polyacrylic acid ester oligomer derives from the Sartomer company of Pennsylvania (Pennsylvania).
Solvent orange 2 A: solvent, Texanol
Organic additive C: additive, CBT (1H-benzo triazole carboxylic acid)
Organic bond A
| Acrylic resin A | 34.78 | Acrylic resin (CarbosetXPD1234), methyl methacrylate 75%, methacrylic acid 25%, Mx=～7000, Tg=120 ℃, acid number=164 |
| Solvent orange 2 A | 46.64 | Texanol |
| Resin B | 1.46 | PVP/VA, vinylpyrrolidone/vinyl acetate copolymer |
| Initiator A | 8.78 | Light trigger, DETX (diethyl thioxanthone) |
| Initiator B | 8.28 | Light trigger, EDAB (ethyl 4-dimethylaminobenzoic acid ester) |
| Inhibitor A | 0.06 | Light stabilizer TAOBN (1,4,4 trimethyls-2,3-diaza-dicyclo [3.2.2]-2-nonene-N, N '-dioxide) |
Organic bond B
| Acrylic resin B | 29.02 | Acrylic resin MMA/ ethyl acrylate/BMA/MAA copolymer, Mw=～30000, acid number=～130 |
| Solvent orange 2 A | 33.85 | Texanol |
| Initiator A | 8.78 | Light trigger, DETX (diethyl thioxanthone) |
| Initiator B | 8.28 | Light trigger, EDAB (ethyl 4-dimethylaminobenzoic acid ester) |
| Inhibitor A | 0.07 | Light stabilizer TAOBN (1,4,4 trimethyls-2,3-diaza-dicyclo [3.2.2]-2-nonene-N, N '-dioxide) |
Silver is stuck with paste component
1, silver is stuck with paste the prescription (wt%) of A and B
| Silver thickener A | Silver thickener B | Explanation | |
| 23.27 | 23.27 | Organic bond C | |
| 6.43 | 6.72 | Organic bond D | |
| 1.96 | 1.89 | Monomer A | Monomer, TMPEOTA (trimethylolpropane ethyoxyl triacrylate) |
| 1.96 | 1.89 | Monomer C | Oligomer, BASF Co., Laromer LR8967 product (acrylic polyester oligomer) |
| 0.15 | 0.15 | Organic additive A | Additive, malonic acid |
| 2.17 | 2.09 | Bi glass dust B | |
| 64.06 | Silver powder A | D50:1.3 μ m spherical powder | |
| 63.99 | Silver powder B | D50:2.0 μ m spherical powder |
Organic bond
| Adhesive C | Adhesive D | Explanation | Chemical name |
| 69.16 | 68.81 | Solvent orange 2 A | Texanol |
| 26.05 | 25.92 | Acrylic resin B | Acrylic resin MMA/ ethyl acrylate/BMA/MAA copolymer, Mw=～30000, acid number=～130 |
| 2.37 | 0.5 | Initiator A | Light trigger, DETX (diethyl thioxanthone) |
| 2.37 | Initiator B | Light trigger, EDAB, (ethyl 4-dimethylamino benzoic acid) | |
| 2.36 | Initator C | Irgacure907 (Ciba), 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl-1-acetone | |
| 2.36 | Initator D | Irgacure 369 (Ciba), 2-benzyl-2-dimethylamino-1-(4-morpholinyl benzene)-1 butanone | |
| 0.05 | 0.05 | Suppress A | Stabilizer, TAOBN (1,4,4 trimethyls-2,3-diaza-dicyclo [3.2.2]-2-nonene-N, N '-dioxide) |
2.Ag the prescription of thickener C and D (wt%)
| Silver thickener C | Silver thickener D | ||
| 18.65 | 18.65 | Organic bonding E | |
| 3.97 | 3.97 | Monomer A | Monomer, TMPEOTA (trimethylolpropane ethyoxyl triacrylate) |
| 4 | 4 | Solvent orange 2 A | Texanol |
| 0.15 | 0.15 | Organic additive C | Addition of C BT (1H-BTA carboxylic acid) |
| 0.5 | 0.5 | Bi glass dust B | |
| 71.34 | Silver powder A | D50:1.3 μ m spherical powder | |
| 71.34 | Silver powder B | D50:2.0 μ m spherical powder | |
| 0.5 | 0.5 | Additive D | BYK Chemie BYK*085 (poly--methyl-alkyl-siloxanes) |
Organic bond E (N97M)
| Wt％ | |
| 52.48 | Texanol |
| 36.01 | Acrylic resin MMA/ETHYLACRYLATE/BMA/MAA copolymer, Mw=～30000, acid number=～130 |
| 5.72 | Irgacure907 (Ciba), 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl propyl-1-ketone |
| 5.72 | Irgacure651 (Ciba), 2,2-dimethoxy-1,2-diethylbenzene-1-ketone |
| 0.07 | Stabilizer, TAOBN (1,4,4 trimethyls-2,3-diaza-dicyclo [3.2.2]-2-nonene-N, N '-dioxide) |
Glass dust is formed the percentage that accounts for the glass composition gross weight
| The glass title | Lead glass powder A | Lead glass powder B | Bi glass dust A | Bi glass dust B | Bi glass dust C | Bi glass dust D | Bi glass dust E | Bi glass dust F | Bi glass dust G |
| PbO | 77 | 62.1 | |||||||
| Bi 2O 3 | 70.0 | 71.8 | 69.8 | 67.5 | 56.8 | 65 | 58.8 | ||
| SiO 2 | 9.1 | 30.8 | 1.5 | 1.0 | 7.1 | 11.5 | 18.2 | 5 | 16.2 |
| Al 2O 3 | 1.4 | 2.6 | 0.5 | 0.5 | 2.1 | 1.5 | 2.3 | 2.3 | |
| B 2O 3 | 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 | ||
| | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| D50(μm) | 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 |
Employed Ru mixture A is Pb among the embodiment
0.75Bi
0.25RuO
3Pyrochlore, the surface area of per unit weight is 11m
2/ g.Ru mixture B is BiRuO
3Pyrochlore, the surface area of per unit weight is 10m
2/ g.
Preparation condition (1)-(5) shown in the preparation condition of electrode such as above-mentioned (C) part among the following embodiment.
Application Example 1-6, Comparative Examples 1-2
Employed Ag conduction paste is that Ag sticks with paste A among these embodiment.
(Ru mixture B, the specific area of Unit Weight is 11m to BiRu pyrochlore powder
2/ g.) mix with the Bi glass dust with different softening point, prepare paste composition sample as shown in table 1.Utilize above-mentioned technology (1)-(5), the part of detecting of preparation bus electrode-black film double-layer structure is also tested.
Table 1
| Composition | Comparative Examples 1 | Comparative Examples 2 | | | Embodiment 3 | | Embodiment 5 | |
| Organic bond 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 orange 2 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 dust A | 16.32 | 16.04 | ||||||
| Pb glass dust B | 24 | 23.59 | ||||||
| Bi glass dust A | 46.34 | |||||||
| Bi glass dust B | 46.34 | |||||||
| Bi glass dust C | 44.36 | |||||||
| Bi glass dust D | 42.66 | |||||||
| Bi glass dust E | 42.66 | |||||||
| Bi glass dust 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 |
Bi glass among the black electrode embodiment is the amorphous glass powder, and softening point range is 448-568 ℃.About 2 μ m) and 2% Bi glass dust B the photosensitive Ag thickener of upper strata Ag electrode contains 60% Ag powder, and (average grain diameter:, Bi glass dust B has softening point minimum in the selected glass dust.
The result provides in table 2.
Table 2
| Comparative Examples 1 | Comparative Examples 2 | | | Embodiment 3 | | Embodiment 5 | | |
| Electric conductor | PbBiRu | BiRu | BiRu | BiRu | BiRu | BiRu | BiRu | BiRu |
| Glass dust Ts (DTA) | 540(calc) | 540(calc) | 448 | 478 | 501 | 534 | 568 | 551 |
| Oven dry thickness/μ m | 6.0 | 6.4 | 6.0 | 5.8 | 5.8 | 6.0 | 6.2 | 7.3 |
| Ag/ black film thickness/μ the m of oven dry | 12.8 | 13.3 | 12.9 | 13.0 | 13.0 | 13.1 | 13.3 | 13.5 |
| Linear resolution (μ m) | 40 | 40 | 40 | 30 | 30 | 40 | 40 | 40 |
| 4 Mil wire thickness/μ m | 6.0 | 7.0 | 6.0 | 6.0 | 6.5 | 7.0 | 6.0 | 7.0 |
| 4 Mil wire edge curl/μ m | 0.0 | 3.8 | 2.0 | 2.0 | 1.0 | 2.0 | Bubble | 2.0 |
| Peel off | In | Slightly | Do not have | In | Slightly | Middle high | Middle high | Middle high |
| The L value that the Ag/ black film is two-layer | 8.9 | 8.99 | 6.68 | 12.15 | 14.4 | 13.59 | 9.07 | 9.56 |
| The L value of one deck black film | 3.97 | 3.88 | 2.52 | 2.61 | 3.7 | 3.61 | 19.6 | 4.87 |
| Resistivity/m Ω/sq@5 μ m | 9.9 | 14.3 | 13.8 | 15.7 | 16.5 | 18.8 | 20.1 | 21.6 |
| The resistance of black electrode (Ω) | 182K | 171K | 267K | 230K | 225K | 203K | 240K | 217K |
By comparing and can know with Comparative Examples 1 and 2 (leaded composition), performance is good down at sintering temperature (550 ℃) for embodiment 1-3 (using low softening point glass dust), has promptly formed practical black electrode.All test performances of embodiment 4-6 (using the high softening-point powder) are not so good.If embodiment 4-6 is at higher roasting temperature, as 600 ℃, they will show superperformance.
Application Example 7-13.Comparative Examples 1a.
Used Ag thickener is Ag thickener A among these embodiment.
In Application Example 1-3, Bi glass dust B display result is good; The high softening-point glass of two kinds of models is difficult to use separately, the weight ratio of described Bi glass dust B be respectively 75/25,50/50 and during 25/75wt% with obtain black electrode sample (seeing Table 3).Having among the embodiment 1-3 the two-layer electrode of Ag electrode obtains estimating.Tested and contained the thickener performance (embodiment 7) of softening point near 550 ℃ Bi glass.
Table 3
| | | Embodiment 9 | | | Embodiment 12 | | |
| 75％ BT26025 25％ BD19 | 50％ BT26025 50％ BD19 | 25％ BT26025 75％ BD19 | 75％ BT26025 25％ BT192 | 50％ BT26025 50％ BT192 | 25％ BT26025 75％ BT192 | ||
| Composition | |||||||
| Organic bond B | 27.2 | 25.9 | 26.3 | 26.8 | 25.9 | 26.3 | 26.8 |
| Monomers B | 6.8 | 6.46 | 6.57 | 6.69 | 6.46 | 6.57 | 6.69 |
| Solvent orange 2 A | 5 | 4.73 | 4.81 | 4.9 | 4.73 | 4.81 | 4.9 |
| Bi glass dust B | 35.7 | 24.2 | 12.3 | 35.7 | 24.2 | 12.3 | |
| Bi glass dust D | 10.2 | 20.8 | 31.7 | ||||
| Bi powder G | 43 | ||||||
| Bi powder 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 |
The result
The result is displayed in Table 4.Table 4 has also shown the measurement result (Comparative Examples 1A) of the leaded black conductive compositions similar to above-mentioned Comparative Examples 1.
Table 4
| | | Embodiment 9 | | | Embodiment 12 | | Comparative Examples 1A (Pb type) | |
| Electric conductor | BiRu | BiRu | BiRu | BiRu | BiRu | BiRu | BiRu | PbBiRu |
| Glass dust Ts (DTA) | 556 | 448/534 | 448/534 | 448/534 | 448/568 | 448/568 | 448/568 | 540 (calculated values) |
| Black film thickness/μ the m of oven dry | 4.0 | 4.2 | 4.1 | 4.0 | 3.9 | 3.8 | 4.0 | 5.0 |
| Oven dry Ag/ black film thickness/μ m | 11.0 | 11.0 | 11.3 | 11.0 | 10.5 | 11.0 | 11.1 | 12.5 |
| Linear resolution (μ m) | 40 | 40 | 40 | 30 | 30 | 40 | 40 | 40 |
| 4 Mil wire thickness/μ m | 5..5 | 5.5 | 5.6 | 6.0 | 5.5 | 5.4 | 5.5 | 5.0 |
| 4 Mil wire edge curl/μ m | 2.6 | 2.5 | 2.5 | 4.3 | 3.3 | 2.5 | 2.4 | 1.1 |
| Peel off | In | In | In | Middle high | Middle high | Middle high | In | Low |
| The L value that the Ag/ black film is two-layer | 15.0 | 11.1 | 13.1 | 15.1 | 11.8 | 14.1 | 15.3 | 9.6 |
| The L value of one deck black film | 14.5 | 4.2 | 4.4 | 5、0 | 4.7 | 4.4 | 13.8 | 6.9 |
| Resistance/m Ω/sq@5 μ m | 22.4 | 22.6 | 17.6 | 21.5 | 18.0 | 15.7 | 20.1 | 11.5 |
| Black film resistance (ohm) | 360k | 366k | 397k | 380k | 412k | 407k | 380k | 430k |
Data show that low softening point glass can mix with the 2nd Bi glass (high softening-point) of different model, and obtains satisfactory performance.Change using different types of high and low softening point glass dust is the effective way that obtains required electrode performance balance.When in some sintering temperature lower-glass compound powder poor performance the time, the performance that may do well at other sintering temperature.
Application Example 14-21, Comparative Examples 1b
Used Ag conducting paste is Ag thickener A among these embodiment.
To account for the percentage by volume of inorganic composition in the total composition be 13-25% to BiRu pyrochlore level among these embodiment.Use the Bi glass dust D that uses high softening-point among Bi glass dust B and the embodiment 18-21 among the embodiment 14-17.Composition provides in table 5.
Table 5
| Sample | Embodiment 14 | Embodiment 15 | Embodiment 16 | Embodiment 17 | Embodiment 18 | Embodiment 19 | Embodiment 20 | Embodiment 21 |
| BiRu 25vol％ | BiRu 21vol％ | BiRu 17vol％ | BiRu 13vol％ | BiRu 25vol％ | BiRu 21vol％ | BiRu 17vol％ | BiRu 13vol％ | |
| Composition | ||||||||
| Organic bond A | 24.95 | 25.16 | 25.36 | 25.59 | 26.6 | 26.34 | 27.28 | 27.62 |
| Monomer A | 6.24 | 6.29 | 6.34 | 6.39 | 6.65 | 6.74 | 6.82 | 6.91 |
| Solvent orange 2 A | 4.57 | 4.6 | 4.64 | 4.68 | 4.87 | 5.5 | 4.99 | 5.06 |
| Organic additive A | 0.83 | 0.84 | 0.85 | 0.85 | 0.89 | 0.9 | 0.91 | 0.92 |
| Organic additive B | 0.16 | 0.17 | 0.17 | 0.17 | 0.18 | 0.18 | 0.18 | 0.18 |
| Bi glass dust B | 43.59 | 46.33 | 49.03 | 51.85 | ||||
| Bi glass dust 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 |
The result
The result is displayed in Table 6.Table 6 has also showed the test result (Comparative Examples 1B) of the leaded black conductive compositions similar to above-mentioned Comparative Examples 1.
| Embodiment 14 | Embodiment 15 | Embodiment 16 | Embodiment 17 | Embodiment 18 | Embodiment 19 | Embodiment 20 | Embodiment 21 | Comparative Examples 1B (Pb type) | |
| Electric conductor | BiRu 25vol％ | BiRu 21vol％ | BiRu 17vol％ | BiRu 13vol％ | BiRu 25vol％ | BiRu 21vol％ | BiRu 17vol％ | BiRu 13vol％ | PbBiRu |
| Glass dust Ts (DTA) | 448 | 448 | 448 | 448 | 534 | 534 | 534 | 534 | 540 (calculated values) |
| Black film thickness/μ the m of oven dry | 4.5 | 5.0 | 5.0 | 4.9 | 5.3 | 5.3 | 5.0 | 5.2 | 5.0 |
| Ag/ black film thickness/μ the m of oven dry | 12.4 | 13.0 | 12.5 | 12.9 | 13.1 | 12.9 | 12.7 | 12.9 | 12.9 |
| Linear resolution (μ m) | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 |
| 4 Mil wire thickness/μ m | 5.8 | 6.0 | 6.0 | 6.0 | 6.5 | 7.0 | 6.3 | 6.3 | 7.5 |
| 4 Mil wire edge curl/μ m | 2.5 | 2.8 | 2.8 | 2.8 | 3.8 | 4.5 | 4.3 | 3.5 | 2.5 |
| Peel off | In | In | In | Middle high | Low | Middle high | Middle high | Middle high | Do not have |
| The L value that the Ag/ black film is two-layer | 5.5 | 7.0 | 11.7 | 15.6 | 13.7 | 15.3 | 16.0 | 19.2 | 9.2 |
| The L value of one deck black film | 3.7 | 3.0 | 5.2 | 9.1 | 4.4 | 5.1 | 8.7 | 18.4 | 5.4 |
| Resistance/m Ω //sq@5 μ m | 14.1 | 12.9 | 11.0 | 15.8 | 19.4 | 20.3 | 16.8 | 17.2 | 9.3 |
| Black film resistance (ohm) | 86k | 190k | 430k | 2M | 29k | 43k | 204k | 9.7M | 754k |
Table 6
Under these test conditions (550 ℃ of following roastings), be better than composition based on Bi glass dust D based on the performance of the composition of Bi glass dust B.High sintering temperature is more suitable in the composition based on Bi glass dust D.The popular tendency of the difference (reducing) of unlicensed tour guide's electricity composition is that the L value increases, and the resistance of black conductive layer increases.
Application Example 22-27, Comparative Examples 1c
In these embodiments, use different binder levels (0,1 and 2wt%Bi glass dust B), preparation Ag conducting paste based on Ag thickener A,, estimated double-decker (referring to above-mentioned) then with black material samples 15 or 19.
The result
The result provides in table 7.The test result (Comparative Examples 1C) that has also shown the leaded black conductive compositions similar in the table to above-mentioned Comparative Examples 1.
Table 7
| Embodiment 22 | Embodiment 23 | Embodiment 24 | Embodiment 25 | Embodiment 26 | Embodiment 27 | Comparative Examples 1C (Pb type) | |
| Glass binder % is (upper strata) in silver | 0％ | 1％ | 2％ | 0％ | 1％ | 2％ | 2％ |
| Black conductive compositions | Embodiment 15 | Embodiment 15 | Embodiment 15 | Embodiment 19 | Embodiment 19 | Embodiment 19 | Comparative Examples 1C |
| Powder Ts (DTA) | 448 | 448 | 448 | 534 | 534 | 534 | 540 (calculated value c) |
| Dried black film thickness/μ m | 5.0 | 5.0 | 5.0 | 5.3 | 5.3 | 5.3 | 5.0 |
| Dry silver/black film thickness/μ m | 13.0 | 12.0 | 13.0 | 12.9 | 12.5 | 12.9 | 12.9 |
| Linear resolution (μ m) | 40 | 40 | 40 | 40 | 40 | 40 | 40 |
| 4 Mil wire thickness/μ m | 5.8 | 5.3 | 6.0 | 6.4 | 6.5 | 7.0 | 7.5 |
| 4 Mil wire edge curl/μ m | 2.3 | 2.5 | 2.8 | 1.8 | 3.5 | 4.5 | 2.5 |
| Peel off | In | In | In | Low | In | Middle high | Do not have |
| The two-layer L value of silver/black film | 9.0 | 8.0 | 7.0 | 11.5 | 14.1 | 15.3 | 9.2 |
| Resistance/m Ω //sq@5 μ m | 11.5 | 10.7 | 12.9 | 8.2 | 16.5 | 20.3 | 9.3 |
Change glass glue component in the Ag electrode, use the black electrode of Bi glass dust B unaffected.On the other hand, Bi glass dust D is a kind of glass dust of high softening-point, uses the electrode of its black electrode composition formation to be subjected to the influence that the glass glue component changes in the Ag electrode.Therefore, forming under the situation of two-layer electrode, not only to also have high conductive layer (bus electrode) to form all be important to black conductive compositions.
Application Example 28-34
Used Ag conducting paste is based on Ag thickener B's among these embodiment.
The Unit Weight specific area of testing the BiRu pyrochlore that is used as unlicensed tour guide's electricity component is to Effect on Performance.Used BiRu pyrochlore has the specific area (3.25-9.02m of different Unit Weights
2/ g), prepared the composition shown in the table 8.
Table 8
| Sample | Embodiment 28 | Embodiment 29 | Embodiment 30 | Embodiment 31 | Embodiment 32 | Embodiment 33 | Embodiment 34 |
| Component | |||||||
| Organic bond A | 27.5 | 27.5 | 27.5 | 27.5 | 27.5 | 27.5 | 27.5 |
| | 6 | 6 | 6 | 6 | 6 | 6 | 6 |
| Solvent orange 2 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 | 47 | 47 | 47 | 47 | 47 | 47 | 47 |
| Bi glass dust B | |||||||
| Ru mixture B SA=3.25 m 2/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 |
The result
The result is as shown in table 9.
Table 9
| Embodiment 28 | Embodiment 29 | Embodiment 30 | Embodiment 31 | Embodiment 32 | Embodiment 33 | Embodiment 34 | |
| Electric conductor | BiRu | BiRu | BiRu | BiRu | BiRu | BiRu | BiRu |
| The specific area of electric conductor and weight ratio m 2/g | 3.25 | 4.04 | 4.91 | 5.71 | 6.61 | 7.86 | 9.02 |
| Glass dust Ts (DTA) | 448 | 448 | 448 | 448 | 448 | 448 | 448 |
| Dried black film thickness/μ m | 3.9 | 4.2 | 3.6 | 3.6 | 4.2 | 3.5 | 4.6 |
| Dried silver/black film thickness/μ m | 13.1 | 12.6 | 13.1 | 13.2 | 12.7 | 12.9 | 13.1 |
| Linear resolution (μ m) | 30 | 30 | 30 | 30 | 30 | 30 | 30 |
| 4 Mil wire thickness/μ m | 6.7 | 7.0 | 6.2 | 5.7 | 5.8 | 5.7 | 6.3 |
| 4 Mil wire edge curl μ m | 2.0 | 2.5 | 1.8 | 2.5 | 2.0 | 2.0 | 2.0 |
| Peel off | Slightly | Slightly | Slightly | Slightly | Slightly | In | In |
| The L value that silver/black film is two-layer | 23.2 | 18.2 | 16.9 | 16.6 | 18.0 | 16.2 | 13.9 |
| The L value of 1 layer of black film | 19.2 | 14.6 | 11.8 | 10.0 | 10.1 | 9.8 | 8.9 |
| Black film/silver-colored resistance/ mΩ/ sq@5μm | 13.4 | 13.2 | 13.1 | 13.4 | 14.1 | 13.9 | 14.8 |
| Black film resistance (ohm) | ＞1G | ＞1G | ＞1G | 10M | 740k | 380k | 210k |
The Unit Weight specific area of BiRu pyrochlore is lower than 4.91m
2/ g, black film resistance become＞1G Ω, and the L value increases.For reducing L value and black film resistance (reducing the Unit Weight specific area of pyrochlore), need to add more pyrochlore component.Therefore, in the present invention, the Unit Weight specific area is greater than 5m
2/ g is preferred, but dispensable.
Application Example 35-38
Used Ag conducting paste is based on Ag thickener C among these embodiment.
The inoganic solids component is to Effect on Performance in the research black electrode thickener.The ratio of the total thickener weight of inoganic solids ingredients constitute in the black electrode thickener is 60-15wt%.The fixed ratio of BiRu pyrochlore is about 0.3.Component is shown in the table 10.
Table 10
| Embodiment 35 | Embodiment 36 | Embodiment 37 | Embodiment 38 | |
| The % solids | 60 | 45 | 30 | 15 |
| Composition | ||||
| Organic bond B | 27.6 | 37.86 | 48.44 | 58.7 |
| Monomers B | 6.9 | 9.47 | 12.13 | 14.7 |
| Solvent orange 2 A | 5 | 6.85 | 8.75 | 10.6 |
| Organic additive C | 0.5 | 0.67 | 0.84 | 1 |
| Bi glass dust B | 46.3 | 34.84 | 23.04 | 11.58 |
| Ru mixture B | 13.7 | 10.31 | 6.81 | 3.42 |
| 100 | 100 | 100 | 100 |
The result
The result is displayed in Table 11.
Table 11
| Embodiment 35 | Embodiment 36 | Embodiment 37 | Embodiment 38 | |
| Electric conductor | BiRu | BiRu | BiRu | BiRu |
| Thickener % solid | 60 | 45 | 30 | 15 |
| Glass dust Ts (DTA) | 448 | 448 | 448 | 448 |
| Black film thickness/μ m after doing | 4.5 | 3.7 | 3.2 | 2.9 |
| Silver/black film thickness/μ m after doing | 13.3 | 12.8 | 12.0 | 12.2 |
| Linear resolution (μ m) | 70 | 110 | 110 | 110 |
| 4 Mil wire thickness/μ m | 7.0 | 6.0 | 6.0 | 5.0 |
| 4 Mil wire edge curl μ m | 12.0 | 14.0 | 11.0 | 2.0 |
| Peel off | Slightly | High | High | Do not have |
| The L value that silver/black film is two-layer | 17.3 | 20.0 | 29.6 | 44.5 |
| The L value of 1 layer of black film | 5.0 | 16.7 | 38.1 | 63.6 |
| Black film/silver-colored resistance/ mΩ / sq@5μm | 9.3 | 6.3 | 5.1 | 6.1 |
| Black film resistance (ohm) | 1.2k | 2.9M | ＞1G | ＞1G |
Along with reducing of inoganic solids constituent content, blackness reduces, and black film resistance increases.When the inoganic solids component is 15wt%, the maximum that blackness reduces.Yet under bigger thickness, the inoganic solids component of 15wt% can produce gratifying black.In embodiment 38, the content of BiRu pyrochlore conductive particle is 3.42wt%, and it is in the low amount place of conducting metal particles constituent content scope 3-50wt%.
Application Example 39-42
Used Ag conducting paste is based on Ag thickener C among these embodiment.
The ratio of the total thickener weight of inoganic solids ingredients constitute is the electrode performance of fixed ratio when about 10wt% of 40-15wt% and BiRu pyrochlore in the research black electrode thickener.Component is displayed in Table 12.
Table 12
| Embodiment 39 | Embodiment 40 | Embodiment 41 | Embodiment 42 | |
| The % solids | 40 | 30 | 20 | 15 |
| Composition | ||||
| Organic bond B | 41.4 | 48.30 | 55.20 | 58.7 |
| Monomers B | 10.4 | 12.10 | 13.90 | 14.7 |
| Solvent orange 2 A | 7.5 | 8.80 | 10.00 | 10.6 |
| Organic additive C | 0.7 | 0.80 | 0.90 | 1 |
| Bi glass dust B | 30 | 20.00 | 10.00 | 5 |
| | 10 | 10.00 | 10.00 | 10 |
| 100 | 100 | 100 | 100 |
The result
The result provides in table 13.
Table 13
| Embodiment 39 | Embodiment 40 | Embodiment 41 | Embodiment 42 | |
| Electric conductor | BiRu | BiRu | BiRu | BiRu |
| Thickener % solid | 40 | 30 | 20 | 15 |
| Glass dust Ts (DTA) | 448 | 448 | 448 | 448 |
| Black film thickness/μ m after doing | 3.5 | 3.3 | 3.0 | 2.5 |
| Silver/black film thickness/μ m after doing | 12.9 | 12.4 | 12.1 | 11.8 |
| Linear resolution (μ m) | 50 | 40 | 50 | 50 |
| 4 Mil wire thickness/μ m | 5.8 | 6.0 | 5.8 | 6.0 |
| 4 Mil wire edge curl μ m | 6.8 | 4.5 | 3.0 | 2.5 |
| Peel off | Slightly | Slightly | Slightly | Slightly |
| The L value that silver/black film is two-layer | 22.6 | 25.0 | 26.9 | 29.0 |
| The L value of 1 layer of black film | 21.5 | 26.7 | 27.5 | 32.6 |
| Black/silver-colored resistance/ mΩ/ sq@5μm | 5.2 | 5.0 | 4.7 | 5.9 |
| Black film resistance (ohm) | 5M | 1.9M | 6.4M | ＞1G |
When electric conductor content 10% the time, the performance of the black electrode that obtains in described glass ingredient scope is rational.
Application Example 43-46
Used Ag conducting paste is based on Ag thickener D among these embodiment.
Studied the performance that inoganic solids thing content in the black conductive compositions is fixed as ratio electrode when 11-14wt% of 26wt% and BiRu pyrochlore.Component is displayed in Table 14.
Table 14
| Embodiment 43 | Embodiment 44 | Embodiment 45 | Embodiment 46 | |
| The % | 10 | 12 | 13 | 14 |
| Composition | ||||
| Organic bond B | 51 | 51 | 51 | 51 |
| Monomers B | 12.8 | 12.8 | 12.8 | 12.8 |
| Solvent orange 2 A | 9.3 | 9.3 | 9.3 | 9.3 |
| Organic additive C | 0.9 | 0.9 | 0.9 | 0.9 |
| Bi glass dust B | 15 | 14 | 13 | 12 |
| | 11 | 12 | 13 | 14 |
| 100 | 100 | 100 | 100 |
The result
The result is shown in the table 15.
Table 15
| Embodiment 43 | Embodiment 44 | Embodiment 45 | Embodiment 46 | |
| Electric conductor | BiRu | BiRu | BiRu | BiRu |
| The % | 11 | 12 | 13 | 14 |
| Glass dust Ts (DTA) | 448 | 448 | 448 | 448 |
| Do back black film thickness/μ m | 3.0 | 3.0 | 3.0 | 3.0 |
| Do back silver/black film thickness/μ m | 12.1 | 12.0 | 12.0 | 12.1 |
| Linear resolution (μ m) | 80 | 80 | 80 | 70 |
| 4 Mil wire thickness/μ m | 7.0 | 6.3 | 6.5 | 6.8 |
| 4 Mil wire edge curl μ m | 1.8 | 2.0 | 2.0 | 1.9 |
| Peel off | Do not have | Do not have | Do not have | Do not have |
| L value silver/black film is two-layer | 26.7 | 24.3 | 23.3 | 22.7 |
| The L value of 1 layer of black film | 22.9 | 19.8 | 17.6 | 17.0 |
| Black film/silver-colored resistance/ mΩ/sq@5 μm | 8.5 | 7.7 | 7.5 | 7.9 |
| Black film resistance (ohm) | 150k | 70k | 40k | 21k |
In all cases, all performances are stable.The L value approximately is 20 o'clock, and it is practical that the black electrode that used electrically conductive composition is made among the embodiment shows.
Application Example 47-50
Used Ag conducting paste is based on Ag thickener D among these embodiment.
Studied the performance that inoganic solids component in the black conductive compositions is fixed as ratio electrode when 14-19wt% of 32wt% and BiRu pyrochlore.Component is displayed in Table 16.
Table 16
| Embodiment 47 | Embodiment 48 | Embodiment 49 | Embodiment 50 | |
| The % electric conductor | 14 | 16 | 18 | 19 |
| Composition | ||||
| Organic bond B | 46.89 | 46.89 | 46.89 | 46.89 |
| Monomers B | 11.78 | 11.78 | 11.78 | 11.78 |
| Solvent orange 2 A | 8.52 | 8.52 | 8.52 | 8.52 |
| Organic additive C | 0.81 | 0.81 | 0.81 | 0.81 |
| Bi glass dust B | 18 | 16 | 14 | 13 |
| Ru mixture B | 14 | 16 | 18 | 19 |
| 100 | 100 | 100 | 100 |
The result
The result provides in table 17.
Table 17
| Embodiment 47 | Embodiment 48 | Embodiment 49 | Embodiment 50 | |
| BiRu | BiRu | BiRu | BiRu | |
| Electric conductor | 14 | 16 | 18 | 19 |
| The % electric conductor | 448 | 448 | 448 | 448 |
| Glass dust | 3.0 | 3.0 | 3.0 | 3.0 |
| Glass dust Ts (DTA) | 12.1 | 12.0 | 12.0 | 12.0 |
| Linear resolution (μ m) | 70 | 70 | 60 | 70 |
| 4 Mil wire thickness/μ m | 7.0 | 7.2 | 7.0 | 7.5 |
| 4 Mil wire edge curl μ m | 0.0 | 0.5 | 0.3 | 1.0 |
| Peel off | Low | Low | Do not have | Do not have |
| The L value that silver/black film is two-layer | 21.0 | 20.1 | 19.3 | 18.0 |
| The L value of 1 layer of black film | 16.6 | 13.5 | 12.9 | 14.2 |
| Black film/silver-colored resistance/ mΩ/sq@5 μm | 8.1 | 7.5 | 7.2 | 7.5 |
| Black film resistance (ohm) | 60k | 25k | 15k | 10k |
In the shown in an embodiment inoganic solids components contents scope, very Shi Yong L value is lower than 20 black electrode and can be designed out.
The foregoing description shows that unleaded black conductive compositions of the present invention can be good at every index of the needed black electrode of balance.
Claims (8)
1, a kind of black conductive compositions, it comprises the following component based on composition total weight percentage:
The conductive metal oxide particle of 3-50 weight %, they are selected from RuO
2, ruthenium Quito oxide and composition thereof;
The organic substance of 25-85 weight %, it includes organic polymer binding agent and organic solvent; With
The unleaded bi-based glass adhesive of one or more of 5-70 weight %, wherein said glass glue comprises the following composition based on glass glue composition total weight percentage: the Bi of 55-85%
2O
3, the SiO of 0-20%
2, 0-5%Al
2O
3, the B of 2-20%
2O
3, the ZnO of 0-20%, one or more of 0-15% are selected from the oxide of BaO, CaO and SrO; And one or more of 0-3% are selected from Na
2O, K
2O, Cs
2O, Li
2The oxide of O and their mixture; And
Wherein, the softening point of described glass glue is 400-600 ℃ of scope;
Described composition characteristics are unleaded or unleaded substantially.
2, the black conductive compositions described in claim 1 is characterized in that, ruthenium Quito oxide is selected from
Bi
2Ru
2O
7, Cu
xBi
2-xRuO
7, GdBiRu
2O
7With their mixture.
3, black conductive compositions as claimed in claim 1, it further comprises the conducting metal particles that is selected from gold, silver, platinum, palladium, copper and composition thereof.
4, black conductive compositions as claimed in claim 1 is characterized in that, described ruthenium Quito oxide specific area is greater than 5m
2/ g.
5, a kind of layer that comprises the composition described in the claim 1, wherein said composition are through handling to remove organic solvent.
6, a kind of black electrode is formed by each described black conductive compositions among the claim 1-3.
7, a kind of single-layer electrodes is formed by the composition described in the claim 3.
8, a kind of flat-panel monitor, it comprises the electrode described in the claim 6.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US66012605P | 2005-03-09 | 2005-03-09 | |
| US60/660,126 | 2005-03-09 | ||
| US60/690,283 | 2005-06-14 | ||
| US11/369,549 | 2006-03-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1881482A true CN1881482A (en) | 2006-12-20 |
Family
ID=37519632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610082024 Pending CN1881482A (en) | 2005-03-09 | 2006-03-09 | Black conductive thick film compositions, black electrodes, and methods of forming thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101641796B (en) * | 2007-04-12 | 2011-03-16 | E.I.内穆尔杜邦公司 | Thick film conductive composition and processes for product obtained thereby and semiconductor device |
| CN101774758B (en) * | 2010-02-05 | 2011-12-28 | 北京科技大学 | Unleaded glass adhesives for unleaded metal electrode sizing agent and preparing method thereof |
-
2006
- 2006-03-09 CN CN 200610082024 patent/CN1881482A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101641796B (en) * | 2007-04-12 | 2011-03-16 | E.I.内穆尔杜邦公司 | Thick film conductive composition and processes for product obtained thereby and semiconductor device |
| CN101774758B (en) * | 2010-02-05 | 2011-12-28 | 北京科技大学 | Unleaded glass adhesives for unleaded metal electrode sizing agent and preparing method thereof |
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