JP5732222B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition useful for forming a fired product pattern such as a high-definition electrode pattern and a black matrix pattern on a plasma display panel (hereinafter abbreviated as “PDP”), and a photosensitive resin composition formed using the same. Relates to the 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 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 space. 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 therein, and three primary colors of visible light are generated. Each cell space is partitioned by ribs arranged in parallel to the substrate surface in the AC type PDP which is currently mainstream. Hereinafter, description will be given with reference to the drawings.

  FIG. 1 partially shows a structural example of a surface discharge PDP having a three-electrode structure for full color display. On the lower surface of the front glass substrate 1, a pair of display electrodes 2a and 2b each comprising a transparent electrode 3a or 3b for discharging and a bus electrode 4a or 4b for lowering the line resistance of the transparent electrode are provided at a predetermined pitch. There are many rows. 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 6 (MgO) is deposited thereon.

    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. Further, phosphor films of three colors of red (14a), blue (14b), and green (14c) are regularly arranged on the inner surface of each discharge space. In full-color display, one pixel is constituted by the phosphor films 14a, 14b, and 14c of the three primary colors of red, blue, and green.

  In the PDP having the above structure, an AC pulse voltage is applied between the pair of display electrodes 2a and 2b, and discharge is performed between electrodes on the same substrate. Moreover, the ultraviolet rays generated by the discharge excite the phosphor films 14a, 14b, 14c of the back substrate 11, and the generated visible light is viewed through the transparent electrodes 3a, 3b of the front glass substrate 1 ( Reflective type).

In recent years, high-definition full-spec high-definition television is becoming mainstream in PDPs, and in order to improve image quality, it is required to increase the density and definition of electrode patterns. On the other hand, patterning by a photolithography method using a photosensitive paste has been performed as a high-definition pattern forming method.
However, since the PDP photosensitive paste contains a large amount of an inorganic material having a very low light transmittance, pattern exposure, line width shrinkage, warpage, etc. are likely to occur during firing due to insufficient photocuring depth during exposure. Such a problem has occurred.

  Also, in order to improve the contrast of the screen, in forming the bus electrode pattern, a black layer of black conductive paste with poor conductivity is printed on the lower layer on the display side, and a white layer of silver paste with good conductivity is further formed thereon. The layer may be printed to form an electrode with a black and white two-layer structure (see, for example, Patent Document 1), but the light transmittance of the upper white layer is poor, so that the lower black layer is sufficiently cured. However, after development, there was a problem that the line width of the black layer became extremely small (undercut) with respect to the line width of the white layer.

JP-A-4-272634

  The present invention has been made in view of the above problems, and the object thereof is to enable formation of a high-definition fired product pattern such as an electrode pattern. It is an object of the present invention to provide a photosensitive resin composition capable of forming a pattern without causing line loss due to undercut.

  In order to achieve the above object, according to one aspect of the present invention, it contains a photopolymerization initiator containing inorganic fine particles, an organic binder, a photopolymerizable monomer, and an oxime ester compound represented by the following general formula (I). The photosensitive resin composition characterized by these is provided. Thereby, a high-definition fired product pattern can be formed. Further, in the case of a bus electrode having a black and white two-layer structure, undercutting can be further reduced.

（式中、Ｒ_１、Ｒ_２はそれぞれ、メチル基、エチル基を表し、Ｒ_３はメチル基またはフェニル基を表し、Ａｒは、結合又はフェニレン、ナフチレン、チエニレンのいずれかを表す。）

(In the formula, R ₁ and R ₂ each represent a methyl group or an ethyl group, R ₃ represents a methyl group or a phenyl group, and Ar represents a bond or any one of phenylene, naphthylene, and thienylene.)

  Moreover, according to the other form of this invention, the baked material pattern formed from such a photosensitive resin composition is provided. Furthermore, according to the other form of this invention, PDP provided with the said baked product pattern is provided.

  According to the photosensitive resin composition of the present invention, a high-definition fired product pattern can be formed, and undercutting can be further reduced in a black and white two-layer bus electrode.

The partial exploded perspective view of a surface discharge type AC type PDP. The schematic fragmentary sectional view which shows an example of the formation process of the bus electrode of a black-and-white two-layer structure.

  The inventors of the present invention have conducted a intensive study in view of the above problems, and as a result, obtained a photosensitive resin composition containing inorganic fine particles, an organic binder, and a photopolymerization initiator containing an oxime ester compound represented by the following general formula (I). As a result, it has been found that a high-definition pattern can be formed, and in the formation of a black and white two-layer bus electrode, it is possible to form a pattern in which undercut is further suppressed, and the present invention has been completed. It was.

（式中、Ｒ_１、Ｒ_２はそれぞれ、メチル基、エチル基を表し、Ｒ_３はメチル基またはフェニル基を表し、Ａｒは、結合又はフェニレン、ナフチレン、チエニレンのいずれかを表す。）

(In the formula, R ₁ and R ₂ each represent a methyl group or an ethyl group, R ₃ represents a methyl group or a phenyl group, and Ar represents a bond or any one of phenylene, naphthylene, and thienylene.)

  In particular, the oxime ester compound represented by the above general formula (I) of the photopolymerization initiator used in the present embodiment is highly sensitive, and has a sensitivity that is equal to or higher than that of a conventional photopolymerization initiator even with a small exposure amount. As a result, a high-definition pattern can be obtained that exhibits excellent curing depth. In addition, in the formation of black and white two-layer bus electrodes, when used in a composition containing a lower black pigment, sufficient photocuring can be performed even under a white layer with poor light transmission. The occurrence of undercut can be suppressed.

Hereinafter, the photosensitive resin composition of the present embodiment and the fired product pattern forming method using the photosensitive resin composition will be described in detail.
First, the photosensitive resin composition of this embodiment is demonstrated in detail.
Examples of the organic binder used in the photosensitive resin composition of the present embodiment include a resin containing a carboxyl group, specifically, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond and an ethylenically unsaturated resin. Any of the carboxyl group-containing resins having no saturated 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) A carboxyl group-containing photosensitive resin obtained by adding an ethylenically unsaturated group as a pendant to a copolymer of an unsaturated carboxylic acid and a compound having an unsaturated double bond.
(3) An unsaturated carboxylic acid is reacted with a copolymer of an epoxy group, a compound having an unsaturated double bond, and a compound having an unsaturated double bond, and a polybasic acid anhydride is added to the resulting secondary hydroxyl group. A carboxyl group-containing photosensitive resin obtained by reaction.
(4) A carboxyl group-containing photosensitive resin obtained by reacting a copolymer of an acid anhydride having an unsaturated double bond and a compound having an unsaturated double bond with a compound having a hydroxyl group and an unsaturated double bond. .
(5) A carboxyl group-containing photosensitive resin obtained by reacting an epoxy compound with an unsaturated monocarboxylic acid and reacting the resulting secondary hydroxyl group with a polybasic acid anhydride.
(6) Reaction of an organic acid having one carboxyl group in one molecule and not having an ethylenically unsaturated bond with the epoxy group of a copolymer of a compound having an unsaturated double bond and glycidyl (meth) acrylate And a carboxyl group-containing resin obtained by reacting the resulting secondary hydroxyl group with a polybasic acid anhydride.
(7) A carboxyl group-containing resin obtained by reacting a hydroxyl group-containing polymer with a polybasic acid anhydride.
(8) A carboxyl group-containing photosensitive resin obtained by further reacting a carboxyl group-containing resin obtained by reacting a hydroxyl group-containing polymer with a polybasic acid anhydride and a compound having an epoxy group and an unsaturated double bond.
In the present specification, “(meth) acrylate” is a general term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

  These organic binders may be used alone or in combination, but in any case, it is preferable to add them in a proportion of 10 to 80% by mass of the total amount of the composition. When the blending amount is less than 10 parts by mass, the distribution of the resin in the film to be formed tends to be non-uniform, and it becomes difficult to obtain sufficient photocurability and photocuring depth, and patterning by selective exposure and development is possible. It becomes difficult. On the other hand, when the amount is more than 80 parts by mass, the distortion of the pattern and the shrinkage of the line width are liable to occur.

  These organic binders preferably have a weight average molecular weight of 1,000 to 100,000, respectively. When the molecular weight is lower than 1,000, the adhesion of the pattern during development is adversely affected. On the other hand, when it is higher than 100,000, development failure tends to occur. More preferably, it is the range of 5,000-70,000.

  Moreover, as an acid value of an organic binder, it is preferable that it is the range of 50-250 mgKOH / g, respectively. 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 it is higher than 250 mgKOH / g, deterioration of the adhesion of the pattern and dissolution of the photocured part (exposed part) are likely to occur during development.

  Moreover, when the organic binder is a resin having photosensitivity, those having a double bond equivalent of 350 to 2,000 are preferable. When the double bond equivalent is smaller than 350, the residue tends to remain during firing. On the other hand, if it is larger than 2,000, the work margin during development is narrow, and a high exposure amount is required during photocuring. More preferably 400 to 1,500.

  The inorganic fine particles used in the photosensitive resin composition of the present embodiment vary depending on the use of the fired product pattern. In the electrode pattern formation, conductive fine particles are used, and in the black electrode pattern formation, the black color is further black. Pigments are also used. Further, a black pigment is used for the black matrix pattern formation, and glass fine particles are used for the partition (rib) pattern formation. In the case of forming the electrode and the black matrix pattern, glass fine particles can be blended as necessary in order to improve the adhesion to the substrate after firing.

Examples of the conductive fine particles include SnO ₂ , In ₂ O ₃ , ITO (Indium Tin Oxide), RuO _{2 in} addition to simple substances such as Ag, Au, Ni, Cu, Al, Sn, Pt, and Ru and alloys thereof. Can be used. These can be used alone or in combination of two or more.

As the shape of such conductive fine particles, various shapes such as a spherical shape, a flake shape, and a dentlite shape can be used. In consideration of optical characteristics and dispersibility, it is preferable to use a spherical shape. Moreover, as an average particle diameter (D50), a thing of 10 micrometers or less is preferable from the point of a line shape. More preferably, it is 5 μm or less. Moreover, it is preferable that it is 0.01-2.0 m < ² > / g as a specific surface area. When the specific surface area is less than 0.01 m ² / g, sedimentation tends to occur during storage. On the other hand, when the specific surface area exceeds 2.0 m ² / g, the oil absorption is increased and the fluidity of the composition is impaired. More preferably, it is 0.1-1.0 m < ² > / g.

  In order to prevent the conductive fine particles 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 such fatty acids include oleic acid, linoleic acid, linolenic acid, stearic acid, and the like.

  The blending amount of such conductive fine particles is preferably 50 to 2,000 parts by mass per 100 parts by mass of the organic binder. When the blending amount is less than 50 parts by mass, it is difficult to obtain good conductivity, and when it exceeds 2,000 parts by mass, pasting tends to be difficult.

As the black pigment, it is preferable to use an inorganic pigment having color tone stability at a high temperature in order to perform high-temperature baking at 300 to 600 ° C. in a baking step described later. Specifically, for example, a black pigment composed of a single metal oxide such as Cu, Fe, Cr, Mn, Co, Ni, Ru, La, Sr and / or a composite oxide composed of two or more metal elements can be used. . In particular, copper-chromium black composite oxide, copper-iron black composite oxide, cobalt tetroxide (Co ₃ O ₄ ), etc. have a dense black film formed after firing and excellent color tone. Are preferably used. These can be used alone or in combination of two or more.

  The average particle diameter (D50) of such a black pigment is preferably 2 μm or less. When the average particle size is 2 μm or less, a dense fired pattern can be formed without impairing adhesion or the like even if added in a small amount. In addition, in the black and white two-layer bus electrode pattern, sufficient interlayer conductivity (interlayer conduction between the transparent electrode and the bus electrode white layer (upper layer)) and blackness can be satisfied at the same time. On the other hand, when the average particle size is larger than 2 μm, the denseness of the fired pattern is deteriorated and the blackness is easily lowered. Moreover, since the hiding power will fall and transparency may appear when it becomes smaller than 0.01 micrometer, More preferably, it is 0.01-1 micrometer.

  The blending amount of such a black pigment is preferably in the range of 10 to 100 parts by mass per 100 parts by mass of the organic binder. When the amount is less than 10 parts by mass, sufficient blackness cannot be obtained after firing. On the other hand, when the amount is more than 100 parts by mass, the light transmittance is lowered and an undercut is likely to occur.

  Moreover, what was previously made into the slurry can also be utilized for a black pigment. 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 composition 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.

  The glass fine particles are preferably low melting point glass frit having a glass transition point (Tg) of 300 to 500 ° C. and a glass softening point (Ts) of 400 to 600 ° C., and lead oxide, bismuth oxide, zinc oxide, lithium oxide Alternatively, those mainly composed of alkali borosilicate are preferably used. The average particle diameter (D50) is preferably 10 μm or less, preferably 5 μm or less from the viewpoint of resolution.

Preferable examples containing lead oxide as a main component include mass percentages based on oxide, 48 to 82% of PbO, 0.5 to 22% of B ₂ O _{3, 3} to 32% of SiO ₂ , and Al ₂ O. ₃ is 0 to 12%, BaO is 0 to 15%, TiO ₂ is 0 to 2.5%, Bi ₂ O ₃ is 0 to 25%, and the softening point is 420 to 580 ° C. Sex frit.

Further, preferred examples of a main component bismuth oxide,% by mass on the oxide basis, _Bi 2 _{O 3} is _6-88%, B 2 _{O 3} is 5 to 30%, SiO ₂ 5 to 25%, An amorphous frit having a composition of Al ₂ O ₃ of 0 to 5%, BaO of 0 to 20%, ZnO of 1 to 20%, and a softening point of 420 to 580 ° C. can be mentioned.

Further, preferred examples of zinc oxide as a main component, in weight percent on the oxide basis, ZnO is 25 to 60%, _{K 2} O is 2 to _15% B 2 _{O 3} is 25 to 45%, SiO ₂ is An amorphous frit having a composition of 1 to 7%, Al ₂ O ₃ of 0 to 10%, BaO of 0 to 20%, MgO of 0 to 10% and a softening point of 420 to 580 ° C. can be mentioned. .

  Such glass fine particles can be blended at a ratio of 200 parts by mass or less, preferably 100 parts by mass or less per 100 parts by mass of the organic binder.

  As the photopolymerization initiator used in the photosensitive resin composition of the present embodiment, it is important to use a photopolymerization initiator containing an oxime ester compound represented by the following general formula (I). As described above, the oxime ester compound is highly sensitive, and even with a small amount of exposure, a sensitivity equal to or higher than that of a conventional photopolymerization initiator can be obtained, so that an excellent curing depth can be obtained and a high-definition pattern can be obtained. Can do. In addition, in the formation of black and white two-layer bus electrodes, when used in a composition containing a lower black pigment, sufficient photocuring can be performed even under a white layer with poor light transmission. The occurrence of undercut can be suppressed.

（式中、Ｒ_１、Ｒ_２はそれぞれ、メチル基、エチル基を表し、Ｒ_３はメチル基またはフェニル基を表し、Ａｒは、結合又はフェニレン、ナフチレン、チエニレンのいずれかを表す。）

(In the formula, R ₁ and R ₂ each represent a methyl group or an ethyl group, R ₃ represents a methyl group or a phenyl group, and Ar represents a bond or any one of phenylene, naphthylene, and thienylene.)

  As for the compounding quantity of such a photoinitiator, 0.5-20 mass parts is preferable with respect to 100 mass parts of organic binders mentioned later. When the amount is less than 0.5 parts by mass, it is difficult to obtain sufficient photocurability of the composition. On the other hand, when the amount exceeds 20 parts by mass, the photocuring of the pattern surface portion is faster than that of the deep portion, so that uneven curing tends to occur. More preferably, it is 1-10 mass parts.

  In addition, when using the photosensitive resin composition of this embodiment for a black-and-white two-layer bus electrode pattern, the photosensitive resin composition containing the said photoinitiator the black pigment which forms a black layer (lower layer) ( The photosensitive resin composition (hereinafter referred to as the “white layer composition”) containing the conductive fine particles forming the white layer (upper layer) is sufficient if it is blended in the “black layer composition”. It is not necessary to add it to.

  This is because the photopolymerization initiator in the lower layer (black layer) coating film diffuses into the upper layer coating layer during coating, drying, or exposure in the bus electrode pattern forming process of a black and white two-layer structure described later. This is considered to be because the crosslinking reaction proceeds in the coating film, or during the exposure, the crosslinking reaction in the lower coating film proceeds to the upper coating film to cure.

Moreover, another photoinitiator, a sensitizer, etc. can be mix | blended as needed.
Examples of such photopolymerization initiators 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- Acetophenones such as diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) -butanone-1, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, etc. Aminoacetophenones; 2-methylanthra Anthraquinones such as non, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc. Thioxanthones; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; or xanthones; (2,6-dimethoxybenzoyl) -2,4,4-pentylphosphine oxide, bis (2,4,4) 6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-2,4,6-trimethylbenzoylphenylphosphinate, etc. Oxime esters; oxime esters such as 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-9-yl] -1- (o-acetyloxime); various peroxides These photopolymerization initiators can be used alone or in combination of two or more.

  Examples of the sensitizer include tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine. These sensitizers can be used, and these sensitizers can be used alone or in combination of two or more.

  In the photosensitive resin composition of the present embodiment, a photopolymerizable monomer is used as necessary in order to promote photocurability and improve developability. In particular, it is effective when the organic binder used in the photosensitive resin composition of the present embodiment is a carboxyl group-containing resin having no ethylenically unsaturated double bond as described above.

  Examples of such photopolymerizable monomers include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polyurethane diacrylate, trimethylolpropane triacrylate, and pentaerythritol. Triacrylate, pentaerythritol tetraacrylate, trimethylolpropane ethylene oxide modified triacrylate, trimethylolpropane propylene oxide modified triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and respective methacrylates corresponding to these acrylates; phthalic acid, Adipic acid, maleic acid, Examples include mono-, di-, tri- or higher polyesters of polybasic acids such as conic acid, succinic acid, trimellitic acid, terephthalic acid, and hydroxyalkyl (meth) acrylate, but are limited to specific ones. These may be used alone or in combination of two or more. Among these photopolymerizable monomers, polyfunctional monomers having two or more (meth) acryloyl groups in one molecule are preferable.

  The amount of such a photopolymerizable monomer is preferably 20 to 100 parts by mass per 100 parts by mass of the organic binder. When the blending amount is less than 20 parts by mass, it is difficult to obtain sufficient photocurability of the composition. On the other hand, when the amount exceeds 100 parts by mass, the photocuring of the pattern surface part is faster than the deep part. Therefore, unevenness in curing tends to occur.

An appropriate amount of a solvent can be blended in order to form a paste by diluting the photosensitive resin composition of the present embodiment so that it can be easily applied to a substrate or the like.
Examples of such solvents include 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 Glycol ethers such as monomethyl ether, dipropylene 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, diethylene glycol monomethyl ether acetate, 2,2,4-to Esters such as methyl-1,3-pentanediol monoisobutyrate; alcohols such as ethanol, propanol, ethylene glycol, propylene glycol and terpineol; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum naphtha, water Examples include petroleum-based solvents such as petroleum naphtha and solvent naphtha, and these can be used alone or in combination of two or more.

  In addition, in order to improve the storage stability of the photosensitive resin composition, it is preferable to add as a stabilizer a compound having an effect such as complexing with a metal or oxide powder as a component of inorganic fine particles or salt formation.

  Such stabilizers include various organic acids such as malonic acid, adipic acid, formic acid, acetic acid, acetoacetic acid, citric acid, stearic acid, maleic acid, fumaric acid, phthalic acid, phosphoric acid, phosphorous acid, hypochlorous acid. Various phosphoric acid compounds such as phosphoric acid, methyl phosphate, ethyl phosphate, butyl phosphate, phenyl phosphate, ethyl phosphite, diphenyl phosphite, mono (2-methacryloyloxyethyl) acid phosphate (inorganic phosphoric acid, Organic phosphoric acid) and acids such as boric acid can be used, and these can 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.

  If necessary, polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, thickeners such as fine silica, organic bentonite, montmorillonite, silicones, fluorines, polymers, etc. Known additives such as antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents and the like can be blended.

Next, a fired product pattern forming method using the photosensitive resin composition of the present embodiment will be described in detail.
The photosensitive resin composition of the present embodiment may be laminated on the substrate when it is previously formed into a film, but in the case of a paste, an appropriate application such as screen printing, bar coater, blade coater, etc. It is applied to a substrate, for example, a glass substrate which is a front substrate of a PDP by a method, and then, for example, in a hot air circulation drying furnace, a far-infrared drying furnace, etc. at about 60 to 120 ° C. for about 5 to 40 minutes in order to obtain touch dryness Dry and evaporate the solvent to obtain a tack-free coating. Thereafter, exposure, development and firing are performed to form a predetermined fired product pattern.

As the exposure step, contact exposure and non-contact exposure using a negative mask having a predetermined exposure pattern are possible. As a light source used for exposure, 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 step, a spray method, an immersion method, or the like is used. Examples of the developer include aqueous metal alkali solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium silicate, and aqueous amine solutions such as monoethanolamine, diethanolamine, and triethanolamine. In particular, a dilute alkaline aqueous solution having a concentration of about 1.5% by mass or less is preferably used, but the carboxyl group of the carboxyl group-containing resin in the composition is saponified, and the uncured part (unexposed part) is removed. The developer is not limited to the developer as described above. 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 developed substrate is subjected to a heat treatment at about 400 to 600 ° C. in the air or a nitrogen atmosphere to form a desired fired product pattern. In addition, it is preferable to set the temperature increase rate at this time to 20 degrees C / min or less.

A method of forming a bus electrode having a black and white two-layer structure will be described in detail with reference to FIG.
First, as shown in FIG. 2A, a front glass substrate 200 on which a transparent electrode 201 such as ITO (Indium tin oxide) is formed in advance by a conventionally known means such as sputtering, ion plating, chemical vapor deposition, electrodeposition or the like. The black layer composition is applied to the substrate, followed by drying to form a tack-free black layer 202.

  Next, as shown in FIG. 2B, a white layer composition is applied onto the formed black layer 202 and then dried to form a tack-free white layer (conductive layer) 203.

  Thereafter, as shown in FIG. 2 (C), a photomask 204 having an exposure pattern is superimposed thereon to expose the black and white two-layer coating film. After the exposure, development is performed with an alkaline aqueous solution to remove the non-exposed portion, and then baking is performed, so that a black layer (lower layer) 202 and a white layer (upper layer) are formed on the transparent electrode 201 as shown in FIG. A bus electrode 205 comprising 203 is formed.

  Further, in the case of a dry film in which the black layer composition and the white layer composition are formed into a film in advance, after laminating them sequentially by thermocompression on the substrate, exposure, development and baking (firing) are performed. It can manufacture by performing each process.

  In addition, a black layer composition is applied on a substrate, and after drying, exposure, development, and baking steps are performed to form a lower layer (black), a white layer composition is applied, followed by drying, exposure, and development. In addition, a method of forming the upper layer (white) by performing each step of baking and baking can also be employed.

  Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but it is needless to say that the present invention is not limited to the following Examples. In the following, “parts” and “%” are based on mass unless otherwise specified.

[Synthesis of alkali-soluble resin (A)]
A flask equipped with a thermometer, a stirrer, a dropping funnel and a 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 azobisisobutyro as a catalyst. Nitrile was added and stirred at 80 ° C. for 7 hours under a nitrogen atmosphere to obtain a solution of the alkali-soluble resin (A). The alkali-soluble resin (A) solution had a weight-average molecular weight of about 10,000, an acid value of 95 mgKOH / g, and a solid content of 57%.
In addition, the measurement of the weight average molecular weight of the obtained alkali-soluble resin (A) (copolymer resin) was performed using Shimadzu pump LC-6AD and Showa Denko column Shodex (registered trademark) KF-804, KF-803, KF- Measurement was performed by high performance liquid chromatography using three 802s.

  Using the alkali-soluble resin (A) synthesized by the above method, the components shown in Table 1 were blended at the blending ratio, stirred with a stirrer, and then kneaded with a three roll mill to form a paste. 4 was obtained.

［備考］
＊１: 1,9-ノナンジオールジアクリレート
＊２: トリメチロールプロパンエチレンオキサイド変性トリアクリレート
＊３： オキシムエステル開始剤（日本化学工業所社製）
＊４： オキシムエステル開始剤 エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(O-アセチルオキシム)（チバ・ジャパン社製）
＊５： 平均粒径（D50）2.2μｍ、最大粒径（D max）6.3μｍ、比表面積0.3ｍ^２/ｇ
＊６： 四三酸化コバルト 平均粒径（D50）0.3μｍ
＊７： Bi₂O₃ 50%、B₂O₃ 16%、ZnO 14%、SiO₂ 2%、BaO 18% 熱膨張係数α₃₀₀＝86×10^-7/℃、ガラス軟化点501℃
＊８： レベリング・消泡剤 モダフロー
＊９：リン酸エステル系安定剤
＊10： ジエチレングリコールモノメチルエーテルアセテート

[Remarks]
* 1: 1,9-nonanediol diacrylate * 2: Trimethylolpropane ethylene oxide modified triacrylate * 3: Oxime ester initiator (manufactured by Nippon Chemical Industry Co., Ltd.)
* 4: Oxime ester initiator Etanone, 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (Ciba Japan)
* 5: Average particle size (D50) 2.2 μm, maximum particle size (D max) 6.3 μm, specific surface area 0.3 m ² / g
* 6: Cobalt tetroxide average particle size (D50) 0.3μm
* 7: 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 ° C
* 8: Leveling and antifoaming agent Modaflow * 9: Phosphate ester stabilizer * 10: Diethylene glycol monomethyl ether acetate

<Production of evaluation substrate>
(Single layer coating)
Application and drying:
Compositions 1 to 4 shown in Table 1 are each printed on a glass substrate with a 200 mesh polyester screen and dried at 100 ° C. for 20 minutes in an IR drying oven to form a film with good touch drying properties. These were used as evaluation substrates.

(Black and white two-layer coating)
Application and drying:
Compositions 2 and 4 shown in Table 1 are each printed on a glass substrate with a 300 mesh polyester screen and dried at 100 ° C. for 20 minutes in an IR drying oven to form a black coating on the substrate. did.
Next, composition 1 was used for the black coating film using composition 2, composition 3 was used for the black coating film using composition 4, and the entire surface of the black coating film was coated using a 200 mesh polyester screen. And dried in an IR drying oven at 100 ° C. for 20 minutes to form a two-layer black and white film having good touch-drying properties. These were used as evaluation substrates.

[Evaluation of electrode of single layer coating and black matrix pattern]
As the electrode pattern, the evaluation of the resolution was performed on the evaluation substrate of the single layer coating produced using the compositions 1 and 3 of the present embodiment and the evaluation substrate of the black matrix pattern produced using the compositions 2 and 4. It was.

<Evaluation>
Resolution (residual thin line);
The evaluation substrate was exposed to light using a metal halide lamp as a light source so that the integrated light amount on the composition was 100 mJ / cm ^2, and then developed using a 0.4% aqueous sodium carbonate solution at a liquid temperature of 30 ° C. Was developed for 15, 20, 25, 30 and 35 seconds, washed with water and dried with an air knife. Thereafter, the remaining lines were observed, and the line having the minimum width that remained without defects was defined as the resolution. The evaluation results are shown in Table 2.

［備考］
＊１：ブラックマトリックス

[Remarks]
* 1: Black matrix

  Examples 1 and 2 are cases where the photosensitive resin composition of the present embodiment was applied to an electrode pattern (single layer) and a black matrix pattern. In Comparative Examples 1 and 2 using a conventional photosensitive resin composition, It can be seen that the resolution (line width) is improved.

[Evaluation of black and white two-layer bus electrode pattern]
As a black-and-white two-layer bus electrode, an evaluation board in which the composition 1 and the composition 2 of the present embodiment are the upper layer (white layer) and the lower layer (black layer) is used as Example 3, and the composition 3 and the composition are used. The evaluation board | substrate of 4 combinations was set as the comparative example 3, and resolution was evaluated by the above-mentioned method. The evaluation results are shown in Table 3.

  Example 3 is a case where the photosensitive resin composition of the present embodiment is applied to a black and white two-layer bus electrode. Compared with Comparative Example 3 using a conventional photosensitive resin composition, the resolution (residual fine wire) ) Is improved.

DESCRIPTION OF SYMBOLS 1,200: Front glass substrate 2a, 2b: Display electrode 3a, 3b, 201: Transparent electrode 4a, 4b, 205: Bus electrode 5: Transparent dielectric layer 6: Protective layer 11: Back glass substrate 12: Rib (partition)
13: Address electrodes 14a, 14b, 14c: Phosphor film 202: Black layer (lower layer)
203: White layer (upper layer, conductive layer)
204: Photomask

Claims (8)

A black and white two-layer structure formed by exposing a black and white two-layer coating film comprising an inorganic fine particle, an organic binder, and a photopolymerization initiator containing a compound represented by the following general formula (I) A photosensitive resin composition for forming.

(In the formula, R ₁ and R ₂ each represent a methyl group or an ethyl group, R ₃ represents a methyl group or a phenyl group, and Ar represents a bond or any one of phenylene, naphthylene, and thienylene.)   Furthermore, the photopolymerizable monomer is included, The photosensitive resin composition for black-and-white two-layer structure formation of Claim 1 characterized by the above-mentioned.   The photosensitive resin composition for forming a black and white bilayer structure according to claim 1, wherein the inorganic fine particles include glass fine particles.   The said inorganic fine particle contains a black pigment, The photosensitive resin composition for black-and-white two-layer structure formation as described in any one of Claim 1 or Claim 3 characterized by the above-mentioned.   The said inorganic fine particle contains electroconductive fine particle, The photosensitive resin composition for black-and-white two-layer structure formation as described in any one of Claims 1-3 characterized by the above-mentioned.   A fired product pattern obtained using the photosensitive resin composition for forming a black and white two-layer structure according to any one of claims 1 to 5.   A plasma display panel comprising the fired product pattern according to claim 6.   From the lower layer which consists of a baking thing of the photosensitive resin composition for black-and-white two-layer structure formation of Claim 4 on a front substrate, and the baking thing of the photosensitive composition for black-and-white two-layer structure formation of Claim 5 A plasma display panel comprising a fired product having an upper two-layer structure.

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