JP2008070661A - Photosensitive paste composition and baked material pattern formed using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive paste composition capable of forming a baked material pattern such as an electrode pattern of high accuracy showing an excellent hardening depth. <P>SOLUTION: The photosensitive paste composition comprises (A) inorganic fine particles, (B) an organic component comprising a photopolymerizable compound and (D) a photopolymerization initiator, wherein (D-1) a specific compound and (D-2) a compound represented by formula (1) and/or a compound represented by formula (2) are used together as the photopolymerization initiator (D) and the combination ratio of the compound (D-2) is <50 mass% to the total mass of the photopolymerization initiator (D). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is a photosensitive paste composition useful for forming a detailed electrode pattern, black matrix pattern, barrier rib pattern and dielectric pattern on a plasma display panel (hereinafter abbreviated as PDP), and is formed using the same. This relates to a fired product pattern.

  The PDP is a flat display that displays images and information using light emission by plasma discharge. The principle of color display by this PDP is that plasma discharge is generated in the cell space (discharge space) between the opposing electrodes formed on the front glass substrate and the rear glass substrate separated by ribs (partition walls), and each cell. The phosphor formed on the inner surface of the rear glass substrate is excited by ultraviolet rays generated by the discharge of a gas such as He or Xe enclosed in the space to generate visible light of the three primary colors. Hereinafter, it will be briefly described with reference to the accompanying drawings.

  FIG. 1 partially shows an example of the structure of a surface discharge PDP having a full color display and a three-electrode structure. On the lower surface of the front glass substrate 1, a large number of a pair of display electrodes 2a and 2b, each consisting of transparent electrodes 3a and 3b for discharging and bus electrodes 4a and 4b for reducing the line resistance of the transparent electrodes, are formed at a predetermined pitch. It is lined up. On these display electrodes 2a and 2b, a transparent dielectric layer 5 (low melting point glass) for accumulating charges is formed by printing and baking, and a protective layer (MgO) 6 is deposited thereon. . The protective layer 6 has a role of protecting the display electrode, maintaining a discharge state, and the like. On the other hand, on the rear glass substrate 11, striped ribs (partitions) 12 partitioning the discharge space and a plurality of address electrodes (data electrodes) 13 arranged in each discharge space are arranged in a predetermined pitch. Yes. In addition, on the inner surface of each discharge space, phosphor films of three colors of red (14a), blue (14b), and green (14c) are regularly arranged, and in full color display, as described above, red, blue The three primary color phosphor films 14a, 14b, and 14c constitute one pixel.

  In the PDP having the above structure, an alternating pulse voltage is applied between the pair of display electrodes 2a and 2b to cause discharge between the electrodes on the same substrate.

  In the PDP having the above structure, ultraviolet light generated by discharge excites the phosphor films 14a, 14b, and 14c of the back substrate 11, and the generated visible light is viewed through the transparent electrodes 3a and 3b of the front substrate 1. (Reflective type).

  In recent years, a PDP having such a structure has been required to have higher density and higher definition in pattern processing in order to improve image quality. Therefore, patterning by photolithography has been performed.

  However, since the PDP photosensitive paste contains a large amount of an inorganic material having a very low light transmittance, the pattern is liable to shrink, warp, warp, or the like during firing due to insufficient photocuring depth during exposure. There was a problem.

  The present invention has been made in order to solve the above-described problems of the prior art, and is a photosensitive paste capable of forming a fired product pattern such as an electrode pattern having high accuracy and excellent curing depth. An object is to provide a composition.

In order to achieve the above object, according to the first aspect of the present invention, the composition contains (A) inorganic fine particles, (B) an organic binder, (C) a photopolymerizable monomer, and (D) a photopolymerization initiator. A photosensitive paste composition comprising (D-1) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and / or 2- () as a photopolymerization initiator (D) (Dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone and (D-2) a compound represented by the following formula (1) and / or Or the compound shown by following formula (2) is used together, and the photosensitive paste composition whose compounding rate of a compound (D-2) is less than 50 mass% with respect to the total mass of a photoinitiator (D). Provided.

  In one embodiment of the present invention, the mass ratio between the compound (D-1) and the compound (D-2) is in the range of 95: 5 to 60:40.

  Furthermore, according to another aspect of the present invention, there is provided a fired product pattern selected from a partition pattern, a dielectric pattern, an electrode pattern and a black matrix pattern of a plasma display panel formed from such a photosensitive paste composition. The

  The photosensitive paste composition of the present invention may be in the form of a paste or may be in the form of a dry film previously formed into a film.

  The photosensitive paste composition of this invention is excellent in photocurability and resolution, and shows the outstanding photocuring depth. As a result, non-uniformity of photocuring is less likely to occur, so that warping and line width shrinkage during firing are less likely to occur, and pattern processing with a high aspect ratio and high accuracy is possible. Therefore, when manufacturing a plasma display panel, a fired product pattern having a high aspect ratio and high accuracy can be formed with high yield and high productivity.

Hereinafter, each component of the photosensitive paste composition of this invention is demonstrated.
The content of the inorganic fine particles (A) varies depending on the desired fired product pattern. First, in the case of electrode pattern formation, conductive powder (conductive metal powder or / and metal oxide) is used, but it is preferable to use an appropriate amount of glass fine particles in combination in order to improve firing properties as described later. Further, when forming a black electrode pattern, a black pigment is also used. On the other hand, in the case of a black matrix pattern, glass fine particles and a black pigment are used, and glass fine particles are used for forming the partition pattern and the dielectric pattern.

  As the glass fine particles, those having a glass transition point (Tg) of 300 to 500 ° C. and a glass softening point (Ts) of 400 to 600 ° C., for example, those mainly composed of lead oxide, bismuth oxide, zinc oxide or lithium oxide are suitable. Can be used. From the viewpoint of resolution, it is preferable to use glass powder having an average particle size of 10 μm or less, preferably 5 μm or less.

  The black pigment in the inorganic fine particles (A) is used when black is required for the firing pattern, and one or more metals such as Co, Ni, Cu, Fe, Mn, Al, Ru, La, Sr, etc. A black pigment made of an oxide can be added. As the pigment, it is desirable to use fine particles having an average particle diameter of 2 μm or less, preferably 0.1 μm or more and 1 μm or less. This is because when the average particle size is 2 μm or less, a dense fired film can be formed without impairing adhesion and the like even with a small amount of addition, and sufficient blackness can be obtained. On the other hand, when the average particle diameter of the black fine particles is larger than 2 μm, the denseness of the fired film is deteriorated, and the blackness is easily lowered. On the other hand, if the thickness is smaller than 0.1 μm, the hiding power may be reduced and a transparency may appear. Therefore, the thickness is more preferably 0.1 μm or more.

  In addition, a black pigment that has been made into a slurry in advance can also be used. In this case, the organic solvent used for the slurry can be arbitrarily selected, but it is desirable to use the same type of solvent as that used in the paste in order to prevent solvent shock. Moreover, although the density | concentration of a slurry can be selected arbitrarily, when workability | operativity etc. are considered, 50-80 mass% is preferable.

Examples of the conductive metal powder or metal oxide in the inorganic fine particles (A) include silver (Ag), gold (Au), nickel (Ni), copper (Cu), aluminum (Al), tin (Sn), platinum ( In addition to simple substances such as Pt) and ruthenium (Ru) and their alloys, tin oxide (SnO ₂ ), indium oxide (In ₂ O ₃ ), ITO (Indium Tin Oxide), ruthenium oxide (RuO ₂ ), etc. may be used. it can. These can be used alone or as a mixed powder of two or more.

  Various shapes such as a spherical shape, a flake shape, and a dentlite shape can be used as the shape of the conductive metal powder or metal oxide. However, in consideration of optical characteristics and dispersibility, it is preferable to use a spherical shape. Further, the average particle size is preferably 10 μm or less, preferably 5 μm or less from the viewpoint of the line shape. In order to prevent the conductive metal powder from being oxidized, to improve the dispersibility in the composition, and to stabilize the developability, it is particularly preferable to treat Ag, Ni, and Al with a fatty acid. Examples of fatty acids include oleic acid, linoleic acid, linolenic acid, and stearic acid.

  The proportion of the conductive metal powder or metal oxide is appropriately 50 to 2000 parts by mass when the total amount of components in the paste other than the inorganic fine particles (A) is 100 parts by mass. When the blending amount of the conductive metal powder or metal oxide is less than 50 parts by mass, the conductor circuit line width shrinkage or disconnection tends to occur. On the other hand, when the blending amount exceeds 2000 parts by mass, light transmission is impaired. It is difficult to obtain sufficient photocurability of the composition. Furthermore, in order to improve the strength of the film after firing and the adhesion to the substrate, the glass fine particles as described above can be added at a ratio of 1 to 30 parts by mass per 100 parts by mass of the conductive powder.

  Next, the organic binder (B) will be described. Examples of the organic binder (B) include a resin having a carboxyl group. Specifically, any of a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond and a carboxyl group-containing resin having no ethylenically unsaturated double bond 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 an unsaturated carboxylic acid and a compound having an unsaturated double bond;
(2) An epoxy group of a copolymer of unsaturated carboxylic acid and glycidyl (meth) acrylate was produced by reacting an organic acid having one carboxyl group in one molecule and no ethylenically unsaturated bond. A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride with a secondary hydroxyl group;
(3) A carboxyl group-containing resin obtained by reacting a hydroxyl group-containing polymer with a polybasic acid anhydride.

  Such a carboxyl group-containing photosensitive resin and a carboxyl group-containing resin may be used alone or in combination, but in any case, they are blended in a proportion of 10 to 80% by mass of the total amount of the composition. It is preferable. When the blending amount of these organic binders is less than the above range, the distribution of the resin in the film to be formed tends to be non-uniform, and it is difficult to obtain sufficient photocurability and photocuring depth, and selective exposure and development. Makes patterning 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 film during development may be adversely affected. On the other hand, when the molecular weight is higher than 100,000, development defects are 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. On the other hand, when the acid value is higher than 250 mgKOH / g, the adhesion of the film is deteriorated during development and the photocured part (exposure Part) is liable to occur, which is not preferable. 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 may be required at the time of photocuring.

  Next, the photopolymerizable monomer (C) will be described. This photopolymerizable monomer is imparted to the photocurability of the paste (for example, effective when the above carboxyl group-containing resin having no ethylenically unsaturated double bond is used), promoting the photocurability of the paste, and developing Used to improve the performance.

  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 ratio of such photopolymerizable monomer (C) is suitably 20 to 100 parts by mass per 100 parts by mass of the organic binder (B) (carboxyl group-containing photosensitive resin and / or carboxyl group-containing resin). is there. When the blending ratio 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 light on the surface portion is larger than the deep portion of the film. Since curing becomes faster, uneven curing tends to occur.

In the present invention, (D-1) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and / or 2- (dimethylamino)-is used as the photopolymerization initiator (D). 2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone and (D-2) a compound 1,2-octanedione represented by the following formula (1) , 1- [4- (phenylthio)-, 2- (O-benzoyloxime) and / or the compound represented by the following formula (2), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl]-, 1- (O-acetyloxime) is used in combination, and the compounding ratio of the compound (D-2) is 50% by mass with respect to the total mass of the photopolymerization initiator (D). Is less than.

  As a result of intensive studies by the inventors, it is important to use the compound (D-1) and the compound (D-2) together as a photopolymerization initiator in order to obtain a higher-definition photosensitive paste. In order to realize such technical significance, it is important that the compounding ratio of the compound (D-2) is less than 50% by mass with respect to the total mass of the photopolymerization initiator (D). Some have also found it. That is, the balance between the deep curability and the surface curability is optimized by setting the compounding ratio of the compound (D-2) to less than 50% by mass with respect to the total mass of the photopolymerization initiator (D). In addition, the resolution at a low exposure amount is improved, and an effect of suppressing halation is obtained.

  In the present invention, the preferred total blending ratio of the photopolymerization initiators (D-1) and (D-2) is based on 100 parts by mass of the organic binder (carboxyl group-containing photosensitive resin and / or carboxyl group-containing resin) solid content. 1-30 parts is suitable. Furthermore, the compounding ratio between the compound (D-1) and the compound (D-2) is 95: 5 to 60:40 (mass ratio). This is preferable in order to more effectively realize halation suppression.

  The compounds represented by the above formulas (1) and (2) are commercially available. For example, Irgacure OXE 01 and OXE02 manufactured by Ciba Specialty Chemicals can be used. (D-1) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and 2- (dimethylamino) -2-[(4-methylphenyl) methyl]- 1- [4- (4-morpholinyl) phenyl] -1-butanone is also commercially available, and for example, Irgacure 369 and Irgacure 379 manufactured by Ciba Specialty Chemicals can be used, respectively.

  When a large amount of glass powder is blended in the photocurable resin composition, the storage stability of the resulting composition is poor, and the coating workability tends to deteriorate due to gelation and fluidity reduction. Therefore, in the composition of the present invention, in order to improve the storage stability of the composition, a compound having an effect of complexing or forming a salt with a metal or oxide powder as a component of the glass powder is added as a stabilizer. It is preferable. Stabilizers include malonic acid, adipic acid, formic acid, acetic acid, acetoacetic acid, citric acid, stearic acid, maleic acid, fumaric acid, phthalic acid and other organic acids, phosphoric acid, phosphorous acid, hypophosphorous acid, Various phosphoric acid compounds (inorganic phosphoric acid, organic phosphoric acid) such as methyl phosphate, ethyl phosphate, butyl phosphate, phenyl phosphate, ethyl phosphite, diphenyl phosphite, mono (2-methacryloyloxyethyl) acid phosphate ), And acids such as boric acid. These may be used alone or in combination of two or more. Such a stabilizer is preferably added at a ratio of 0.1 to 10 parts by mass per 100 parts by mass of the inorganic fine particles.

  When a photopolymerizable monomer is blended in the photosensitive composition, the storage stability of the resulting composition is poor, and the coating workability tends to be poor due to gelation or a decrease in fluidity. Therefore, in the composition of the present invention, it is preferable to add a thermal polymerization inhibitor of a photopolymerizable monomer in order to improve the storage stability of the composition. Examples of the thermal polymerization inhibitor include phenothiazine, naphthoquinone, hydroquinone, N-phenylnaphthylamine, chloranil, pyrogallol, benzoquinone, t-butylcatechol and the like, and these can be used alone or in combination of two or more. Such a stabilizer is preferably added at a ratio of 0.01 to 1 part by mass per 100 parts by mass of the organic binder (solid content).

  In the present invention, the composition is made into a paste by diluting, and the coating process can be easily performed. Subsequently, in order to dry and form a film and to enable contact exposure, an appropriate amount of an organic solvent can be blended. 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.

  The photosensitive paste composition of the present invention may further contain other additives such as silicone-based and acrylic-based defoaming / leveling agents, silane coupling agents for improving film adhesion, etc., if necessary. 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.

  The photosensitive 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, an appropriate coating 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 an electrode circuit having 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 firing 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 conductor pattern. In addition, it is preferable to set the temperature increase rate at this time to 20 degrees C / min or less.

  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.

(Example 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, dipropylene glycol monomethyl ether as a solvent, and azobisiso as a catalyst. Butyronitrile was added, and the mixture was stirred at 80 ° C. for 2 to 6 hours under a nitrogen atmosphere to obtain an organic binder A. This organic binder A had a weight average molecular weight of about 10,000, an acid value of 74 mgKOH / g, and a solid content concentration of 60%. Using this organic binder A, it was blended at the composition ratio shown below, stirred with a stirrer, and then kneaded with a three-roll mill to form a paste. Kneaded meat conditions are 1 kg of sample amount at room temperature for 30 minutes. As the glass powder, Bi ₂ O ₃ 49%, B ₂ 0 ₃ 14%, ZnO 14%, SiO ₂ 6%, BaO 17% were pulverized to a glass transition point of 458 ° C. and an average particle diameter of 1.6 μm. I used something.

Invention Example 1;
Organic binder A 170.0 parts Trimethylolpropane triacrylate 50.0 parts 2- (Dimethylamino) -2-[(4-methylphenyl) methyl]
-1- [4- (4-morpholinyl) phenyl] -1-butanone
5.0 parts 1,2-octanedione, 1- [4- (phenylthio)-,
2- (O-benzoyloxime)] 1.0 part Solvesso # 200 ^* 20.0 parts Silver powder 500.0 parts Glass powder 40.0 parts Phosphate ester 5.0 parts Antifoam (BYK-354, Big Chemie Japan) ) 1.0 part.

Invention Example 2;
Organic binder A 170.0 parts Trimethylolpropane triacrylate 50.0 parts 2- (Dimethylamino) -2-[(4-methylphenyl) methyl]
-1- [4- (4-morpholinyl) phenyl] -1-butanone
5.0 parts ethanone, 1- [9-ethyl-6- (2-methylbenzoyl)-
9H-carbazol-3-yl]-, 1- (O-acetyloxime)
1.0 part Solvesso # 200 ^* 20.0 parts Silver powder 500.0 parts Glass powder 40.0 parts Phosphate ester 5.0 parts Antifoaming agent (BYK-354, Big Chemie Japan) 1.0 part.

Invention Example 3;
Organic binder A 170.0 parts Trimethylolpropane triacrylate 50.0 parts 2- (Dimethylamino) -2-[(4-methylphenyl) methyl]
-1- [4- (4-morpholinyl) phenyl] -1-butanone
3.6 parts ethanone, 1- [9-ethyl-6- (2-methylbenzoyl)-
9H-carbazol-3-yl]-, 1- (O-acetyloxime)
2.4 parts Solvesso # 200 ^* 20.0 parts Silver powder 500.0 parts Glass powder 40.0 parts Phosphate ester 5.0 parts Antifoaming agent (BYK-354, Big Chemie Japan) 1.0 part.

Comparative composition example 1
Organic binder A 170.0 parts Trimethylolpropane trimethacrylate 50.0 parts 2-Benzyl-2-dimethylamino-1- (4-
Morpholinophenyl) butanone-1 6.0 parts Solvesso # 200 20.0 parts Silver powder 500.0 parts Glass powder 40.0 parts Phosphate ester 1.0 part Antifoam (BYK-354, Big Chemie Japan) 0 copies.

Comparative composition example 2
Organic binder A 170.0 parts Trimethylolpropane trimethacrylate 50.0 parts 2- (Dimethylamino) -2-[(4-methylphenyl) methyl]
-1- [4- (4-morpholinyl) phenyl] -1-butanone
6.0 parts Solvesso # 200 ^* 20.0 parts Silver powder 500.0 parts Glass powder 40.0 parts Phosphate ester 1.0 part Antifoaming agent (BYK-354, Big Chemie Japan) 1.0 part.

Comparative composition example 3
Organic binder A 170.0 parts Trimethylolpropane triacrylate 50.0 parts Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl)-
9H-carbazol-3-yl]-, 1- (O-acetyloxime)
6.0 parts Solvesso # 200 ^* 20.0 parts Silver powder 500.0 parts Glass powder 40.0 parts Phosphate ester 5.0 parts Antifoaming agent (BYK-354, Big Chemie Japan) 1.0 part.

Comparative composition example 4
Organic binder A 170.0 parts Trimethylolpropane triacrylate 50.0 parts 2- (Dimethylamino) -2-[(4-methylphenyl) methyl]
-1- [4- (4-morpholinyl) phenyl] -1-butanone
3.0 parts ethanone, 1- [9-ethyl-6- (2-methylbenzoyl)-
9H-carbazol-3-yl]-, 1- (O-acetyloxime)
3.0 parts Solvesso # 200 ^* 20.0 parts Silver powder 500.0 parts Glass powder 40.0 parts Phosphate ester 5.0 parts Defoamer (BYK-354, Big Chemie Japan) 1.0 part (* Solvesso # 200: Aromatic hydrocarbon, manufactured by ExxonMobil Corporation).

  About each paste of composition example 1-2 obtained in this way and comparative composition example 1-4, the line shape after image development, resolution (remaining), sensitivity, line shape after baking, and baking residue evaluated. The evaluation method is as follows.

Resolution:
The evaluation paste was applied on the entire surface of the glass substrate using a 300-mesh polyester screen, and then dried at 80 ° C. for 30 minutes in a hot-air circulating drying oven to form a film having good touch drying properties. . Thereafter, a metal halide lamp is used as the light source, and exposure is performed using a striped negative mask having a line width of 10 to 100 μm and a space width of 100 μm so that the integrated light quantity on the composition is 50 to 300 mJ / cm ^2. Development was carried out using a 0.5 wt% Na ₂ CO ₃ aqueous solution at 0 ° C. and washed with water. Finally, the temperature was raised at 5 ° C./min in an air atmosphere and baked at 600 ° C. for 5 minutes to produce a substrate. The evaluation method examined the thinnest thing formed in the 10-100 micrometers line.

Line shape:
The line shape after development was evaluated by observing a pattern line (L / S = 100 μm / 300 μm) completed until development with a microscope and checking for irregularities in the line and no wrinkles. About the line shape after baking, the pattern which complete | finished to baking was observed with the microscope, and it evaluated by whether there was no irregular variation in a line, and there was no twist. The evaluation criteria are as follows.

A: There is no irregular variation and there is no chipping or twisting.

○: There is no irregular variation, and there is almost no chipping or twisting.

Δ: Some irregular variation, chipping or twisting

X: Irregular variation, chipping or twisting.

Step tablet sensitivity:
For sensitivity, read the remaining number of steps on the step tablet (Kodak No. 2) after development.

Firing residue:
The line (L / S = 100 μm / 300 μm) of the pattern finished up to firing was observed with a microscope, and evaluated by whether there was no firing residue on the side surface. The evaluation criteria are as follows.

○: Almost no firing residue.

Δ: There is a little baking residue.

X: There are many baking residues.

  As is clear from the results shown in Table 1, the paste according to the composition of the present invention is excellent in the depth of curing as compared with the paste of the comparative composition, and therefore can form a high-definition pattern with high sensitivity even at a low exposure amount. I understood.

(Example 2) Storage stability Composition examples 1 and 2 obtained in Example 1 were stored at 40 ° C. for 10 days and then tested in the same manner as in Example 1. As a result, the same good results as in Example 1 were obtained. Results were obtained.

The partial exploded perspective view of a surface discharge type AC type PDP.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Front glass substrate 2a, 2b Display electrode 3a, 3b Transparent electrode 4a, 4b Bus electrode 5 Transparent dielectric layer 6 Protective layer 10 Black pattern 11 Back glass substrate 12 Rib 13 Address electrode 14a, 14b, 14c Phosphor film 100 For PDP Front substrate 100

Claims (3)

A photosensitive paste composition containing (A) inorganic fine particles, (B) an organic binder, (C) a photopolymerizable monomer, and (D) a photopolymerization initiator, and (D) as a photopolymerization initiator (D) -1) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and / or 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [ 4- (4-morpholinyl) phenyl] -1-butanone and (D-2) a compound represented by the following formula (1) and / or a compound represented by the following formula (2) are used in combination. The photosensitive paste composition whose compounding ratio of 2) is less than 50 mass% with respect to the total mass of a photoinitiator (D).

  The photosensitive paste composition according to claim 1, wherein the mass ratio of the compound (D-1) and the compound (D-2) is in the range of 95: 5 to 60:40.   A fired product pattern selected from a partition pattern, a dielectric pattern, an electrode pattern, and a black matrix pattern of a plasma display panel formed from the photosensitive paste composition according to claim 1.

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