JP2009149461A - Paste composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a paste composition capable of forming a black layer which has a low contact resistance value between an Ag layer (white layer) and a transparent electrode in a bus electrode of a white/black two-layer structure and is excellent in the black degree. <P>SOLUTION: The paste composition comprises a black inorganic oxide (A) and an organic binder (B), wherein the black inorganic oxide (A) is represented by the composition formula: Ni<SB>3x</SB>Co<SB>3y</SB>Mn<SB>3(1-x-y)</SB>O<SB>4</SB>(0≤x≤0.6, 0≤y≤0.6, 0.4≤(1-x-y)). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an improvement in a paste composition containing a black inorganic oxide.

  Paste compositions containing black inorganic oxides are widely used for paints, inks, toners, rubber / plastics, electronic materials and the like.

  Known black inorganic oxides that are black pigments include carbon black, copper / iron / manganese composite oxide, and cobalt trioxide. Among them, cobalt tetroxide is known to be excellent in blackness that does not exhibit redness or yellowness, and is stable even under severe use conditions thermally and mechanically.

  In recent years, with respect to black pigments and the like used for these materials, there has been an increasing demand for black pigments that are not reddish or yellowish.

  In response to such a requirement, Patent Document 1 discloses that cobalt cobalt hydroxide or water is used for the purpose of improving blackness which is stable even under severely and thermally severe use conditions and does not exhibit redness or yellowness. Cobalt oxide is heated in an oxidizing atmosphere and fired at a temperature of 200 ° C. to less than 500 ° C., then cooled to a temperature of less than 200 ° C., and heated again in an oxidizing atmosphere at a temperature of 500 ° C. to 800 ° C. A black pigment made of tribasic cobalt tetraoxide powder obtained by firing is disclosed. However, the cobalt tetroxide disclosed in Patent Document 1 has not fully satisfied the recent high demand for blackness.

In addition, when the paste composition using tribasic cobalt oxide is used for the lower layer (black layer) paste of the bus electrode having a black and white two-layer structure, the contact resistance value between the Ag layer (white upper layer) and the transparent electrode is always desired. Does not have low enough to. That is, the paste composition used for the above applications may cause problems such as uneven emission of electrodes, image defects, and increased power consumption. For this reason, the paste composition from which the contact resistance value of Ag layer and a transparent electrode becomes lower was calculated | required.
JP 2003-138160 A, Claims, etc.

  Specifically, the subject of the present invention is a paste composition capable of forming a black layer having a lower contact resistance value between an Ag layer (white layer) and a transparent electrode in a bus electrode having a black and white two-layer structure and having excellent blackness. To provide things.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a composite oxide containing manganese having a specific composition, and have completed the present invention.

  That is, the paste composition of the present invention that can solve the above problems is as follows.

(1) black inorganic oxide (A), and contains an organic binder (B), a black inorganic oxide (A) _{is, Ni 3x Co 3y Mn 3 (} 1-x-y) O 4 (0 ≦ x ≦ 0.6, 0 ≦ y ≦ 0.6, 0.4 ≦ (1-x−y)).

(2) A fired product pattern formed on a substrate, comprising a fired product of the paste composition according to (1).

(3) The fired product layer formed on the substrate is Ni _3x Co _3y Mn _{3 (1-xy)} O ₄ (0 ≦ x ≦ 0.6, 0 ≦ y ≦ 0.6, 0.4 ≦ A fired product pattern comprising a black inorganic oxide (A) represented by a composition formula of (1-xy)).

(4) The fired product pattern of (2) or (3) constitutes a bus electrode on the front plate of the plasma display panel.

  In the claims and the specification, the values of x, y, and z are based on the values of Co, Ni, and Mn contents measured by ICP emission analysis.

  According to the present invention, for example, there is provided a paste composition that can form a black layer having a lower contact resistance value between an Ag layer (white layer) and a transparent electrode in a black and white two-layer bus electrode and having excellent blackness. can do.

Hereinafter, the paste composition of the present invention will be described in detail.
Black inorganic oxide (A)
The black inorganic oxide of the present invention is substantially Ni _3x Co _3y Mn _{3 (1-xy)} O ₄ (0 ≦ x ≦ 0.6, 0 ≦ y ≦ 0.6, 0.4 ≦ (1 -Xy)). FIG. 1 is a Ni—Co—Mn ternary phase diagram showing the composition. Within the scope of the present invention, both the contact resistance value between the Ag layer and the transparent electrode in the black and white two-layer bus electrode and the blackness of the black layer are excellent. For example, the contact resistance value is as low as 15 to 25Ω, and the blackness of the black layer is 6 to 12 for the L value, 0 to 3 for the a value, and 0 to 4 for the b value. Here, when the L value, the a value, and the b value are out of the above ranges, redness and yellowness become strong, and the blackness of the black layer deteriorates. On the other hand, when the composition of the black inorganic oxide deviates from the scope of the present invention, either or both of the contact resistance value and the blackness are inferior to the present invention.

  The black inorganic oxide according to the present invention deteriorates in blackness by generating an impurity phase such as NiO exhibiting a green color. Therefore, the impurity phase of NiO is 2θ = 62 in the X-ray diffraction of the black inorganic oxide. It is preferable that the intensity ratio of the diffraction peak having an intensity of .9 degrees and a maximum intensity of 2θ = 61 to 66 degrees is smaller than 0.9. Furthermore, it is particularly preferable that the intensity ratio is smaller than 0.7.

  Further, the black inorganic oxide particles in the paste composition according to the present invention have a primary particle size D50 (meaning a particle size having a cumulative frequency of 50% in the number distribution curve of the primary particle size) of 0.10. It is preferably ˜0.60 μm, more preferably 0.16 to 0.60 μm, still more preferably 0.20 to 0.40 μm, and the maximum primary particle size is 2.0 μm or less. Is preferred. When the primary particle size D50 is smaller than 0.10 μm, the redness and yellowness of the particles become strong, and when the primary particle size D50 is larger than 0.60 μm, the blackness of the particles becomes low. Further, when the maximum primary particle size is larger than 2.0 μm, the blackness of the particles tends to be lowered, and therefore the maximum primary particle size is preferably 2.0 μm or less.

  Such a black inorganic oxide particle is a mixed aqueous solution of nickel salt, cobalt salt and manganese salt in a reaction vessel, while maintaining a reaction temperature of 30 to 70 ° C. under an inert gas atmosphere and adding sufficient stirring. An aqueous solution of ammonia as a complexing agent is added to the solution, and an aqueous solution of an alkali metal hydroxide is added so as to maintain the pH at 9 to 12 to produce a nickel cobalt manganese composite hydroxide. The product can be obtained by solid-liquid separation, water washing and drying, followed by heat treatment at a temperature of 600 to 800 ° C. in an air atmosphere or an oxygen atmosphere.

  According to the paste composition using the black inorganic oxide of the present invention, the contact resistance value between the Ag layer and the transparent electrode can be further lowered without affecting the specific resistance value of the bus electrode. As a result, by suppressing the contact resistance value to a low level, it is possible to improve the light emission unevenness of the panel, improve the light emission characteristics, and reduce the power consumption.

  In consideration of dispersibility and blackness, the black inorganic oxide (A) is 1 to 30% by mass, preferably 5 to 25% by mass in the paste.

  Moreover, it is preferable that the black inorganic oxide (A) is contained in the black layer at a ratio of 10 to 100% by mass in consideration of the contact resistance value and the blackness after firing.

Organic binder (B)
Next, as the organic binder (B), a carboxyl group-containing resin, specifically, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond and an ethylenically unsaturated double bond. Any carboxyl group-containing resin that is not used can be used. Examples of the resin (which may be either an oligomer or a polymer) that can be suitably used include the following.

(1) A carboxyl group-containing resin obtained by copolymerizing (a) an unsaturated carboxylic acid and (b) a compound having an unsaturated double bond (2) (a) an unsaturated carboxylic acid and (b) unsaturated A carboxyl group-containing photosensitive resin obtained by adding an ethylenically unsaturated group as a pendant to a copolymer of a compound having a double bond (3) (c) a compound having an epoxy group and an unsaturated double bond ( b) A carboxyl group obtained by reacting a copolymer of a compound having an unsaturated double bond with (a) an unsaturated carboxylic acid, and reacting the resulting secondary hydroxyl group with (d) a polybasic acid anhydride. Containing photosensitive resin (4) (e) a copolymer of an acid anhydride having an unsaturated double bond and (b) a compound having an unsaturated double bond, (f) having a hydroxyl group and an unsaturated double bond Obtained by reacting compounds Carboxyl group-containing photosensitive resin (5) (g) A carboxyl obtained by reacting an epoxy compound with (h) an unsaturated monocarboxylic acid and reacting the resulting secondary hydroxyl group with (d) a polybasic acid anhydride Group-containing photosensitive resin (6) (b) An epoxy group of a copolymer of an unsaturated double bond and a glycidyl (meth) acrylate copolymer, (i) having one carboxyl group in one molecule, ethylene (D) a carboxyl group-containing resin (7) (j) obtained by reacting an organic acid not having a polymerizable unsaturated bond and reacting the resulting secondary hydroxyl group with (d) a polybasic acid anhydride (d) ) A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride (8) (j) A carboxyl group-containing resin obtained by reacting a hydroxyl group-containing polymer with (d) a polybasic acid anhydride, (c) Epoxy Carboxyl group-containing photosensitive resin obtained by further reacting a group and a compound having an unsaturated double bond The carboxyl group-containing photosensitive resin and the carboxyl group-containing resin as described above may be used alone or in combination. However, in any case, these are preferably blended in a proportion of 10 to 80% by mass of the total amount of the composition. When the blending ratio of these organic binders is less than the above range, the distribution of the resin in the coating film to be formed tends to be non-uniform, and it is difficult to obtain sufficient photocurability and photocuring depth, and selective exposure. Patterning by development becomes difficult. On the other hand, if it is more than the above range, it is not preferable because the pattern during baking and the shrinkage of the line width are likely to occur.

  The carboxyl group-containing photosensitive resin and the carboxyl group-containing resin each have a weight average molecular weight of 1,000 to 100,000, preferably 5,000 to 70,000, and an acid value of 50 to 250 mgKOH / g, and In the case of a carboxyl group-containing photosensitive resin, those having a double bond equivalent of 350 to 2,000, preferably 400 to 1,500 can be suitably used. When the molecular weight of the resin is lower than 1,000, the adhesion of the coating film during development is adversely affected. On the other hand, when the molecular weight is higher than 100,000, poor development is likely to occur, which is not preferable. On the other hand, when the acid value is lower than 50 mgKOH / g, the solubility in an alkaline aqueous solution is insufficient, and development failure tends to occur. This is not preferable because dissolution of the exposed portion occurs. Further, in the case of a carboxyl group-containing photosensitive resin, if the double bond equivalent of the photosensitive resin is less than 350, a residue is likely to remain at the time of baking, whereas if it is greater than 2,000, a work margin at the time of development. Is narrow, and a high exposure amount is required at the time of photocuring.

Water-soluble dispersant
The water-soluble dispersant suitably used in the present invention is an amphoteric dispersant having an acid value of 30 mgKOH / g or more and an amine value of 20 mgKOH / g or more. By using such a dispersant, a paste having high dispersibility and a long-term stability can be obtained. The reason for this is that when a dispersant having an acid value of 30 mgKOH / g or an amine value of less than 20 mgKOH / g is used, the dispersibility between the black inorganic oxide and the organic binder is lowered, and thus the developability is lowered. Residues are likely to occur. In addition, the storage stability is lowered, and separation tends to occur over time.

  Moreover, the dispersing agent used for this invention uses a water-soluble thing. The reason is that if the dispersant is not water-soluble, when the inorganic oxide slurry is stored for a long period of time, separation between the solvent in the slurry and the inorganic oxide is likely to occur, and the inorganic oxide is highly stable for a long period of time. This is because it is difficult to form a slurry.

  The water-soluble dispersant preferably has a 10% by mass aqueous solution pH of 6.0 to 10.0. When the pH of the 10% by weight aqueous solution of the dispersant is less than 6.0, the inorganic oxide in the black inorganic oxide paste reacts with the dispersant, so that the inorganic oxide in the black inorganic oxide paste when stored for a long period of time. May occur. On the other hand, when the pH of the 10% by weight aqueous solution of the dispersant is higher than 10.0, the black inorganic oxide paste tends to be separated from the solvent and inorganic oxide during long-term storage of the black inorganic oxide paste, and the dispersibility is high. It will not be a long-term stable black inorganic oxide paste.

  Examples of the dispersant having such characteristics include Disperbyk-180, Disperbyk-187, and Disperbyk-191 (all of which are trade names, manufactured by BYK Chemie).

  In consideration of dispersibility and blackness, the water-soluble dispersant is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the organic binder (B). More preferably, it is 0.5-10 mass parts, More preferably, it is 1-6 mass parts.

Photopolymerizable monomer
Next, the paste composition of the present invention can be blended with a photopolymerizable monomer in order to promote photocurability and improve developability of the composition. Examples of the photopolymerizable monomer include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polyurethane diacrylate, trimethylolpropane triacrylate, and pentaerythritol triacrylate. Acrylate, pentaerythritol tetraacrylate, trimethylolpropane ethylene oxide modified triacrylate, trimethylolpropane propylene oxide modified triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and each methacrylate corresponding to the above acrylate; phthalic acid, adipine Acid, maleic acid, itacone Mono-, di-, tri- or higher polyesters of polybasic acids such as succinic acid, trimellitic acid, terephthalic acid and the like and hydroxyalkyl (meth) acrylates, but are limited to specific ones. It is not a thing, and these can be used individually or in combination of 2 or more types. Among these photopolymerizable monomers, polyfunctional monomers having two or more acryloyl groups or methacryloyl groups in one molecule are preferable.

  The blending amount of such a photopolymerizable monomer is suitably 20 to 100 parts by mass per 100 parts by mass of the organic binder (carboxyl group-containing photosensitive resin and / or carboxyl group-containing resin) (B). When the blending amount of the photopolymerizable monomer is less than the above range, it is difficult to obtain sufficient photocurability of the composition. On the other hand, when the amount exceeds the above range, the surface portion is more than the deep portion of the coating film. Unevenness of curing is likely to occur due to faster photocuring.

Photopolymerization initiator
Next, the paste composition of the present invention can further contain a photopolymerization initiator. Examples of the photopolymerization initiator include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 Acetophenones such as phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1 Aminoacetophenones such as-(4-morpholinophenyl) -butanone-1; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; 2,4- Thioxanthones such as methylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenones such as benzophenone; or xanthones; , 6-Dimethoxybenzoyl) -2,4,4-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-2 Phosphine oxides such as 1,4,6-trimethylbenzoylphenyl phosphinate; various peroxides, etc., and these known and commonly used photopolymerization initiators may be used alone or in combination of two or more. It can be used Te Align.

  The mixing ratio of these photopolymerization initiators is suitably 1 to 30 parts by mass, preferably 5 parts per 100 parts by mass of the organic binder (carboxyl group-containing photosensitive resin and / or carboxyl group-containing resin) (B). ˜20 parts by mass.

  In addition, the above photopolymerization initiator includes three kinds such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine. It can be used in combination with one or more of photosensitizers such as secondary amines. Furthermore, when a deeper photocuring depth is required, a titanocene photopolymerization initiator such as Irgacure 784 manufactured by Ciba Specialty Chemicals, which starts radical polymerization in the visible region, and leuco dyes are cured as necessary. It can be used in combination as an auxiliary agent.

  In the present invention, when a large amount of inorganic filler or glass powder is blended in the paste composition, the storage stability of the resulting composition is poor, and the coating workability tends to be poor due to gelation or fluidity deterioration. Accordingly, in the composition of the present invention, in order to improve the storage stability of the composition, a compound effective for complexing or forming a salt with a metal or oxide powder as a component of an inorganic filler or glass powder, such as an organic acid. It is preferable to add a stabilizer such as The amount of the stabilizer added is preferably 0.1 to 10 parts by mass per 100 parts by mass of the inorganic filler or glass powder.

Glass powder
The paste composition of the present invention contains glass powder having a softening point of 400 to 600 ° C., if necessary, in a quantitative ratio that does not impair the characteristics of the paste composition of the present invention, in order to improve the adhesion of the pattern after firing. can do. The glass powder preferably has a glass transition point (Tg) of 300 to 500 ° C. and a glass softening point (Ts) of 400 to 600 ° C. From the viewpoint of resolution, it is preferable to use glass powder having an average particle size of 20 μm or less, preferably 5 μm or less.

  As such a glass powder, an amorphous frit mainly composed of lead oxide, bismuth oxide, zinc oxide or the like can be suitably used.

  The glass powder can be blended in the paste in an amount of 1 to 25% by mass, preferably 5 to 20% by mass.

Other ingredients
In the present invention, an appropriate amount of an organic solvent can be blended as a diluent for pasting the composition or a diluent for adjusting the viscosity according to various coating steps. Specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, di Glycol ethers such as propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate Acetic acid esters such as ethanol, propanol, ethylene glycol, propylene glycol And alcohols such as terpineol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These may be used alone or in combination of two or more. Can be used.

  If necessary, the paste composition of the present invention further contains other additives such as silicone-based and acrylic-based antifoaming / leveling agents, silane coupling agents for improving the adhesion of coating films, and the like. You can also. Furthermore, if necessary, fine particles such as metal oxides, silicon oxides, boron oxides, and the like, which are known and commonly used antioxidants, and as binding components to the substrate during firing may be added.

Use of paste composition
The paste composition of the present invention may be laminated on a substrate when it is previously formed into a film, but in the case of a paste-like composition, an appropriate application method such as screen printing, bar coater, blade coater, etc. Apply to a glass substrate, for example, a front substrate of a PDP, and then dry in a hot-air circulating drying furnace, a far-infrared drying furnace, etc. for about 5 to 40 minutes at about 60 to 120 ° C. The organic solvent is evaporated to obtain a tack-free coating film. Thereafter, selective exposure, development, and baking are performed to form a predetermined pattern.

As the exposure step, contact exposure and non-contact exposure using a negative mask having a predetermined exposure pattern are possible. As the exposure light source, a halogen lamp, a high-pressure mercury lamp, a laser beam, a metal halide lamp, a black lamp, an electrodeless lamp, or the like is used. The exposure amount is preferably about 50 to 1000 mJ / cm ² .

  As the development process, a spray method, an immersion method, or the like is used. Developers include aqueous alkali metal solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium silicate, and aqueous amine solutions such as monoethanolamine, diethanolamine and triethanolamine, especially about 1.5% by mass or less. A dilute alkaline aqueous solution having a concentration of 1 is preferably used, as long as the carboxyl group of the carboxyl group-containing resin in the composition is saponified and the uncured part (unexposed part) is removed. It is not limited to. Further, it is preferable to perform washing with water and acid neutralization in order to remove unnecessary developer after development.

  In the baking step, the substrate after development is subjected to heat treatment at about 400 to 600 ° C. in air or in a nitrogen atmosphere to form a desired pattern. In addition, it is preferable to set the temperature increase rate at this time to 20 degrees C / min or less.

(Examples and comparative examples according to the present invention)
EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. “Parts” and “%” are based on mass unless otherwise specified.

  Using the black inorganic oxide slurry obtained in the following production example, the organic binder obtained in the synthesis example, and the glass slurry obtained in the production example, a paste was formed and evaluated.

(Preparation of Ni-Co-Mn black inorganic oxide)
Nickel sulfate, cobalt sulfate, and manganese sulfate are dissolved in ion-exchanged water so as to have predetermined molar ratios corresponding to the following Examples 1 to 3 and Comparative Example 1-5, and 1.5 mol of nickel, cobalt, and manganese are dissolved. / L metal salt aqueous solution was prepared.

  While controlling the reactor temperature to be 50 ° C. under a nitrogen atmosphere, sufficient stirring was performed in an effective volume 15 L reactor containing 10 L of ion exchange water.

  While adding 1.5 mol / L metal salt aqueous solution and ammonium sulfate aqueous solution dropwise to the reaction vessel performing the stirring, a sodium hydroxide aqueous solution is dropped so as to maintain a pH of 10.8. A composite hydroxide was obtained.

  The spherical nickel cobalt manganese composite hydroxide was heat treated at a firing temperature of 650 ° C. for 5 hours and pulverized to obtain a black inorganic oxide.

  Regarding the Co, Ni, and Mn contents of the obtained black inorganic oxide, the black inorganic oxide as a sample was dissolved in hydrochloric acid, and Co, Ni, and Mn were measured by ICP emission analysis.

For the primary particle size D50, a 20,000-70,000-fold photograph was taken with an FE SEM (field emission scanning electron microscope), and the ferret diameter of 200 primary particles was measured.

(Preparation of black inorganic oxide slurry)
15 kg of the black inorganic oxide obtained above was mixed into a mixed solution of 5.09 kg of solvent tripropylene glycol monomethyl ether and a dispersant BYK180 (trade name, manufactured by BYK Chemie) 0.21 kg. The mixture was stirred for 1 hour using a stirrer so as not to remain in the mixed solution to obtain a preliminary slurry.
It was confirmed that 1.12 kg of the solvent tripropylene glycol monomethyl ether was present in the bead mill vessel and piping.
The preliminary slurry thus obtained was pumped to a rotating peripheral speed 12 m / s bead mill (LMZ4 type manufactured by Ashizawa Finetech Co., Ltd.) filled with zirconia beads having a diameter of 0.1 mm and a filling rate of 85%. It was introduced and circulated and wet pulverized to obtain a black inorganic oxide slurry.
The end point was determined when the average particle size of the slurry reached 0.26 to 0.31 μm in the particle size measurement by laser diffraction method.

(Synthesis of organic binder (B-1))
A flask equipped with a thermometer, stirrer, dropping funnel, and reflux condenser is charged with methyl methacrylate and methacrylic acid in a molar ratio of 0.87: 0.13, diethylene glycol monomethyl ether acetate as a solvent, and azobisisobutyrate as a catalyst. Ronitrile was added and stirred at 80 ° C. for 2 to 6 hours under a nitrogen atmosphere to obtain an organic binder (B-1). This organic binder (B-1) had a weight average molecular weight of about 30,000, an acid value of 90 mgKOH / g, and a solid content of 50%. In addition, the measurement of the weight average molecular weight of the obtained organic binder (B-1) (copolymer resin) was performed using Shimadzu pump LC-6AD and Showa Denko column Shodex (registered trademark) KF-804, KF-803, Measurement was performed by high performance liquid chromatography using three KF-802s.

(Production of glass slurry)
As the glass powder, Bi ₂ O ₃ 50%, B ₂ O ₃ 16%, ZnO 14%, SiO ₂ 2%, BaO 18%, thermal expansion coefficient α ₃₀₀ = 86 × 10 ⁻⁷ / ° C., glass softening point 501 The one at ° C was used.
Further, grinding in a bead mill, the Mitsui Mining using manufactured SC50 Co., media size using the ZrO ₂ beads made of 0.3～0.8Mmfai, at a rotation speed of 2,000～3,300Rpm,. 3 to Milling was carried out for 9 hours.
In addition, the Horiba laser diffraction / scattering type particle size distribution measuring device LA-920 was used for the particle size measurement.
After roughly pulverizing the glass powder, it was filtered with a 300 mesh screen, and 70 parts by mass of this glass powder and 29.16 parts by mass of 2,2,4-trimethyl-1,3-pentanediol monobutyrate were added thereto. As a dispersant, 0.14 parts by mass of BYK-410 and 0.7 parts by mass of BYK-182 were added and finely pulverized with a bead mill. D50: 1.0 μm, Dmax: 3.9 μm glass powder content Produced a 70% by weight slurry.
The produced glass slurry was further filtered through a SUS 200 × 1400 twill mat mesh, but no change was observed in the particle size distribution.

(Composition Example 1)
Organic binder (B-1) 100.0 parts diethylene glycol monomethyl ether acetate 110.0 parts trimethylolpropane EO-modified triacrylate 30.0 parts diventaerythritol hexaacrylate 15.0 parts polyester acrylate (trade name M-7100, Toa Gosei) 50.0 parts leveling agent (trade name Modaflow, manufactured by Monsanto) 3.0 parts phosphoric acid ester 1.0 part glass slurry 43.0 parts black inorganic oxide slurry (black inorganic oxide composition Ni: Co: Mn = 20: 20: 60) 67.0 parts
10.0 parts of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one
2,4-Diethylthioxanthone 3.0 parts
4,4-bis (diethylamino) benzophenone 1.0 part γ-methacryloxypropyltrimethoxysilane 3.0 parts (Composition Example 2)
Composition other than replacing black inorganic oxide slurry (black inorganic oxide composition Ni: Co: Mn = 20: 20: 60) with black inorganic oxide slurry (black inorganic oxide composition Co: Mn = 50: 50) Pasting was performed with the same composition as in Example 1.

(Composition Example 3)
Black inorganic oxide slurry (black inorganic oxide composition Ni: Co: Mn = 20: 20: 60) was replaced with black inorganic oxide slurry (black inorganic oxide composition Ni: Co: Mn = 10: 45: 45) Except for this, pasting was performed with the same composition as in Composition Example 1.

(Comparative composition example 1)
Black inorganic oxide slurry (black inorganic oxide composition Ni: Co: Mn = 20: 20: 60) was replaced with black inorganic oxide slurry (black inorganic oxide composition Ni: Co: Mn = 33: 33: 33) Except for this, pasting was performed with the same composition as in Composition Example 1.

(Comparative composition example 2)
Black inorganic oxide slurry (black inorganic oxide composition Ni: Co: Mn = 20: 20: 60) was replaced with black inorganic oxide slurry (black inorganic oxide composition Ni: Co: Mn = 20: 60: 20) Except for this, pasting was performed with the same composition as in Composition Example 1.

(Comparative composition example 3)
Black inorganic oxide slurry (black inorganic oxide composition Ni: Co: Mn = 20: 20: 60) was replaced with black inorganic oxide slurry (black inorganic oxide composition Ni: Co: Mn = 60: 20: 20) Except for this, pasting was performed with the same composition as in Composition Example 1.

(Comparative composition example 4)
Black inorganic oxide slurry (black inorganic oxide composition Ni: Co: Mn = 20: 20: 60) was replaced with black inorganic oxide slurry (black inorganic oxide composition Ni: Co: Mn = 70: 10: 20) Except for this, pasting was performed with the same composition as in Composition Example 1.

(Comparative composition example 5)
Black inorganic oxide slurry (black inorganic oxide composition Ni: Co: Mn = 20: 20: 60) was replaced with black inorganic oxide slurry (black inorganic oxide composition Ni: Co: Mn = 0: 100: 0) Except for this, pasting was performed with the same composition as in Composition Example 1.

(Dispersion of paste)
Each paste component of Composition Examples 1 to 3 and Comparative Composition Examples 1 to 5 is blended in a plastic container and stirred with a dissolver at 500 rpm for 10 minutes. Thereafter, the paste was prepared by performing kneaded meat twice with three ceramic rolls.

  A test piece was prepared for each of the photosensitive pastes of the composition examples and the comparative composition examples thus obtained, and the blackness and the contact resistance value were evaluated.

(Test piece preparation method)
Each photosensitive paste for evaluation is applied on the entire surface of a glass substrate using a 300-mesh polyester screen, and then dried at 90 ° C. for 20 minutes in a hot-air circulating drying oven to form a coating film of about 4 μm. did. Next, using an ultra-high pressure mercury lamp as a light source and exposing so that the integrated light quantity on the dried coating film becomes 600 mJ / cm ² , development is performed using a 0.4 wt% Na ₂ CO ₃ aqueous solution at a liquid temperature of 25 ° C. Done, washed with water. The solid film thus obtained was heated to 14 ° C./min. Temperature: baked at 590 ° C. for 10 minutes. A dielectric (trade name: YPT-065F (AP5655AE), manufactured by Asahi Glass Co., Ltd.) was applied over the entire surface of the fired film using a 100 mesh polyester screen. Subsequently, after drying at 90 degreeC for 20 minute (s) with a hot-air circulation type drying furnace, 14 degreeC / min. Temperature: baked at 580 ° C. for 10 minutes to obtain a test piece.

(Measurement of blackness)
About the test piece produced by the said method, the value of L ^* a ^* b ^* color system was measured according to JIS-Z-8729 using the color difference meter (the Minolta camera Co., Ltd. product, CR-221), and the brightness The L ^* value, which is an index representing, was evaluated as an index of blackness. The smaller the L ^* value, the better the blackness.

(Preparation of contact resistance measurement substrate)
On the glass substrate (PD200 manufactured by Asahi Glass Co., Ltd.) on which an ITO film has been formed in advance, each photosensitive paste for evaluation was applied to the entire surface using a 200 mesh polyester screen, and then in a hot air circulation drying oven. The film was dried at 90 ° C. for 20 minutes to form a coating film of about 5 μm. Next, after using an ultra-high pressure mercury lamp as a light source and exposing so that the integrated light quantity on the dried coating film becomes 600 mJ / cm ² , Ag paste (compounding composition will be described later) on the exposed coating film is 200 mesh polyester. It was coated on the entire surface using a screen, and then dried at 90 ° C. for 20 minutes in a hot air circulating drying oven to form a coating film of about 10 μm. Furthermore, using an ultra-high pressure mercury lamp as a light source, pattern exposure was performed on the dried coating film so as to be 400 mJ / cm ² , development was performed using a 0.4 wt% Na ₂ CO ₃ aqueous solution at a liquid temperature of 25 ° C., and washing was performed. . The temperature of the substrate thus obtained was 14 ° C./min. Temperature: baked at 590 ° C. for 10 minutes to obtain a test piece having a pattern as shown in FIG.

(Measurement of contact resistance value)
The firing pattern X in FIG. 2 was used for the measurement of the contact resistance value, and the contact resistance value of this firing pattern was measured ((1) to (5)) using a HIOKI 3540 mΩ HiTester manufactured by HIOKI. The average value was obtained.
The indication “impossible to measure” means that the limit value that can be measured by the measuring instrument is exceeded.

(Measurement of resistivity value)
The firing pattern Y in FIG. 2 was used for measurement of the specific resistance value, and the resistance value of the fired pattern was measured and the specific resistance value was calculated using a Hioki 3540 mΩ Hitester manufactured by HIOKI. The specific resistance value is calculated as follows.

Specific resistance (Ω · cm) = Line resistance (Ω) × film thickness (cm) × line width (cm) / line length (cm)
The indication “impossible to measure” means that the limit value that can be measured by the measuring instrument is exceeded.

The results of blackness measurement, contact resistance value measurement, and specific resistance value measurement are shown in Table 1.

  As is clear from the results shown in Table 1, it was confirmed that by using the photosensitive paste of the present invention, a fired film having good blackness and low contact resistance can be provided.

  In addition, about the composition examples 1-3 of the Example, when the dispersibility of the paste was investigated, it was confirmed that a stable paste with a high dispersibility can be obtained for a long time.

(Composition composition of Ag paste applied on the exposed coating film)
The Ag paste was prepared by blending an organic binder (B-2), silver powder, and the like.

(Synthesis of organic binder (B-2))
In a flask equipped with a thermometer, stirrer, dropping funnel, and reflux condenser, diethylene glycol monoethyl ether acetate as a solvent and azobisisobutyronitrile as a catalyst are added and heated to 80 ° C. in a nitrogen atmosphere. A monomer mixed with methacrylic acid: 0.4 mol and methyl methacrylate: 0.6 mol in a molar ratio is added dropwise over about 2 hours, and further stirred for 1 hour, and then the temperature is raised to 115 ° C. to deactivate. A resin solution was obtained. After cooling this resin solution, tetrabutylammonium bromide was used as a catalyst at 95 to 115 ° C. for 30 hours, and butyl glycidyl ether: 0.4 mol was added with an equivalent amount of carboxyl group of the obtained resin and addition reaction. And cooled. Further, 0.26 mol of tetrahydrophthalic anhydride was added to the OH group of the obtained resin under the conditions of 95 to 105 ° C. and 8 hours, cooled and taken out, and an organic binder having a solid content of 55% (B -2) was obtained.

Silver powder having an average particle size (D50) of 2.2 μm, a maximum particle size (Dmax) of 6.3 μm and a surface area of 0.3 m ² / g was used.

(Ag paste composition)
Organic binder (B-2) 100.0 parts
Diethylene glycol monoethyl ether acetate 90.0 parts
Trimethylolpropane triacrylate 25.0 parts
Trimethylolpropane EO-modified triacrylate 25.0 parts
2-Benzyl-2-dimethylamino-1-
10.0 parts of (4-morpholinophenyl) butan-1-one
450.0 parts of silver powder
Glass slurry 22.0 parts
Phosphate ester 1.0 part
Antifoaming agent (BYK-354: manufactured by Big Chemie Japan) 1.0 part

The Ni-Co-Mn ternary phase diagram showing the composition of the black inorganic oxide according to the present invention (the range within the bold line is the range of the present invention). In the test piece on which the fired pattern was formed, the pattern X was used for measuring the contact resistance value, and the pattern Y was used for measuring the specific resistance value.

Claims (4)

Black inorganic oxide (A), and contains an organic binder (B), a black inorganic oxide (A) _{is, Ni 3x Co 3y Mn 3 (} 1-x-y) O 4 (0 ≦ x ≦ 0.6 And 0 ≦ y ≦ 0.6, 0.4 ≦ (1-xy)). A fired product pattern formed on a substrate, comprising a fired product of the paste composition according to claim 1. The fired product layer formed on the substrate is Ni _3x Co _3y Mn _{3 (1-xy)} O ₄ (0 ≦ x ≦ 0.6, 0 ≦ y ≦ 0.6, 0.4 ≦ (1- A fired product pattern comprising a black inorganic oxide (A) represented by a composition formula of xy)). 4. The fired product pattern according to claim 2, wherein a bus electrode is formed on the front plate of the plasma display panel.

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