JP2006261005A - Method for forming barrier rib for flat display and method for manufacturing flat display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for forming a barrier rib for a flat display, wherein the light exposure margin where problems such as meandering and/or peeling, pattern thickening and/or residual film formation do not occur can be enlarged when forming the barrier rib for the flat display with high definition and high aspect ratio, and wherein the increase of a required light exposure is small. <P>SOLUTION: In the method for forming the barrier rib for the flat display comprising in the following order: a step for forming a first photosensitive composition layer by applying and drying a first photosensitive paste at least to a glass substrate; a step for forming a second photosensitive composition layer by applying and drying a second photosensitive paste to the first photosensitive composition layer; a step for exposuring and developing the first photosensitive composition layer and the second photosensitive composition layer at the same time; and a step for baking, the characteristic value γ<SB>1</SB>of the sensitivity of the first photosensitive paste and the characteristic value γ<SB>2</SB>of the sensitivity of the second photosensitive paste satisfy γ<SB>1</SB>>γ<SB>2</SB>. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for forming partition walls provided in a flat display such as a plasma display, a field emission display, and a fluorescent display tube, and a method for manufacturing the flat display.

  In recent years, development of flat displays such as a plasma display, a field emission display, a fluorescent display tube, a liquid crystal display device, an electroluminescence display, and a light emitting diode has been rapidly advanced. Among these, a gas discharge type display such as a plasma display or a fluorescent display tube requires an insulating partition for partitioning the discharge space. A field emission display such as a field emission display requires an insulating partition for isolating the gate electrode from the cathode electrode. In the formation of insulating partition walls such as these plasma displays and field emission displays, materials and processing methods capable of patterning inorganic materials such as glass fine particles with high accuracy are required.

Particularly with respect to plasma displays, it is an indispensable technique for increasing the brightness of plasma displays by forming high-definition and high-aspect-ratio barrier ribs to ensure a wider discharge space. Conventionally, a method of forming a pattern using a photosensitive paste has been proposed as a method for performing fine pattern processing of an inorganic material (for example, Patent Document 1). The cross-sectional shape of the plasma display partition is preferably rectangular in order to ensure a wider discharge space and suppress charge leakage to adjacent cells, that is, the side of the partition is perpendicular to the substrate surface. However, in a photosensitive paste coating film containing inorganic fine particles in a dispersed manner, it is difficult to avoid scattering of exposure light, so that the bottom of the partition wall is insufficiently cured at a rectangular exposure amount, and meandering or peeling tends to occur. . On the other hand, when the exposure amount is increased for the purpose of sufficiently curing the bottom of the coating film, the pattern shape becomes thicker due to light scattering and a residual film is easily formed between the patterns. As a result, when forming high-definition and high-aspect-ratio partition walls, problems such as meandering and peeling, pattern pattern thickening, and residual film formation are likely to occur. There is a problem that the amount margin) is narrowed. In order to eliminate such pattern pattern thickening, it has been proposed to add an ultraviolet absorber having light absorption in the ultraviolet region to the paste (for example, Patent Document 2). Absorption of weak scattered light at the bottom of the coating film by adding an ultraviolet absorber can suppress the pattern thickening at the bottom of the partition wall, but since the UV absorber is uniformly present in the coating film, curing Also, the exposure light necessary for the absorption is absorbed, and the sensitivity is lowered, so that there is a problem that the required exposure amount increases. On the other hand, although the photosensitive paste is laminated and applied, and the sensitivity of the lower layer photosensitive paste is made higher than that of the upper layer, a proposal has been made to improve insufficient curing and sensitivity reduction at the bottom of the partition wall (Patent Document 3). When the sensitivity of the lower layer paste is increased, it becomes easy to cure even with weak scattered light, and thus there is a problem that the pattern shape is likely to be thickened at the bottom. As described above, in the formation of high-definition barrier ribs, there has been a problem that the expansion of the exposure amount margin and the suppression of the increase in the required exposure amount have a trade-off relationship.
JP-A-5-342992 (Claim 1) JP-A-8-050811 (Claim 1) JP-A-11-149862 (Claim 1)

  The present invention pays attention to the problems of the prior art described above, and provides an exposure margin that does not cause problems such as meandering, peeling, pattern thickening, and residual film formation when forming a high-definition and high-aspect-ratio flat panel partition. An object of the present invention is to provide a method for forming a partition for a flat panel display that can be enlarged and has a small increase in required exposure.

In order to solve the above problems, the present invention has the following configuration. That is, the present invention includes a step of applying a first photosensitive paste on at least a glass substrate and drying to form a first photosensitive composition layer, and a second photosensitive paste on the first photosensitive composition layer. Coating and drying to form a second photosensitive composition layer, exposing the first photosensitive composition layer and the second photosensitive composition layer simultaneously and developing to form a pattern, A method of forming a partition for a flat panel display including steps of firing the obtained pattern in this order, wherein a sensitivity characteristic value γ ₁ of the first photosensitive paste and a sensitivity characteristic value γ _{2 of} the second photosensitive paste are It is achieved by a method for forming a partition for a flat display, which satisfies the following formula (1).
γ ₁ > γ ₂ (1)

  According to the present invention, when forming a high-definition and high-aspect-ratio flat panel partition, it is possible to expand an exposure margin that does not cause problems such as meandering, peeling, pattern shape thickening, and residual film formation, and necessary exposure. It is possible to provide a method for forming a partition for a flat display capable of suppressing an increase in the amount.

  As a result of intensive studies on a method for forming a partition for a flat panel display that can solve the above-mentioned problems, the inventors have found that this can be achieved by a method for forming a partition as described below.

That is, the present invention includes a step of applying a first photosensitive paste on at least a glass substrate and drying to form a first photosensitive composition layer, and a second photosensitive composition layer on the first photosensitive composition layer. Applying a conductive paste and drying to form a second photosensitive composition layer, simultaneously exposing and developing the first photosensitive composition layer and the second photosensitive composition layer, and firing. The flat panel display forming method includes the steps of performing the steps described above, and the sensitivity characteristic value γ ₁ of the first photosensitive paste and the sensitivity characteristic value γ ₂ of the second photosensitive paste are represented by the following formula (1). It is characterized by.
γ ₁ > γ ₂ (1)
Here, photosensitive means that the chemical structure of the photosensitive organic component changes through reactions such as photocrosslinking, photopolymerization, photodepolymerization, and photo-denaturation when the photosensitive paste is irradiated with actinic rays. To do. The photosensitive paste in the present invention needs to be a negative photosensitive paste that changes its chemical structure upon irradiation with actinic rays and becomes insoluble in the developer. The actinic light mentioned here refers to light in the wavelength region of 250 to 1100 nm that causes such chemical reaction. Specifically, ultraviolet light such as ultra-high pressure mercury lamp and metal halide lamp, visible light such as halogen lamp, helium- Examples of the laser beam include a cadmium laser, a helium-neon laser, an argon ion laser, a semiconductor laser, a YAG laser, and a carbon dioxide laser, and the like. In the present invention, an ultraviolet ray having a wavelength of 300 to 500 nm is used. It can be preferably used.

Further, each of the sensitivity characteristic value gamma _n of photosensitive paste _(n is 1 or 2) is applied to the photosensitive paste, to the coating of the initial thickness d _n0 obtained by drying, exposure with an exposure amount E _n Thereafter, when the remaining film thickness after further development is _dn and the curing start exposure amount is _En0 , it is obtained by the following formula (2).
γ _n = (d _n / d _n0 ) / (logE _n −logE _n0 ) (2)
γ _n can be obtained by the following method. A photosensitive paste is applied and dried, and the thickness of the obtained coating film is measured to obtain _dn0 . Request residual film thickness d _n after development by changing the exposure amount. Next, a characteristic curve is obtained with the horizontal axis representing the common logarithm logE _n of the exposure amount and the vertical axis representing the remaining film ratio d ₀ / dn ₀ . Among these characteristic curves, an approximate straight line is obtained from the data in the range of the remaining film ratio of 20 to 80% by the least square approximation method. The horizontal axis intercept of the approximate straight line corresponds to logE _n0 and the slope corresponds to γ _n .

Therefore, a large γ _n value of the photosensitive paste means that curing does not start at a low exposure amount such as scattered light, and curing proceeds rapidly when a certain threshold value is exceeded. Then, the first photosensitive paste having such a large γ _n value is applied and dried to form the first photosensitive composition layer, and the second photosensitive composition is formed on the first photosensitive composition layer. By coating and drying the product to form a second photosensitive composition layer, and then exposing and developing the two layers simultaneously, a rectangular barrier rib having a wide exposure margin can be obtained. However, increasing γ _n generally involves a decrease in the sensitivity of the photosensitive paste. For example, when a thick film partition such as 100 to 200 μm is formed like a partition of a plasma display, a rectangular shape is obtained. There is a possibility that the required exposure amount will increase significantly.

Therefore, in the present invention, the sensitivity characteristic value γ ₁ of the first photosensitive paste and the sensitivity characteristic value γ ₂ of the second photosensitive paste are solved by the relationship of the following formula (1).
γ ₁ > γ ₂ (1)
That is, by using the first photosensitive paste having a large sensitivity characteristic value γ _n for the lower layer of the photosensitive composition layer in which a lot of scattered light is generated and the pattern thickening is likely to occur, the pattern thickening is suppressed, By using the second photosensitive paste having a small sensitivity characteristic value γ _n as the upper layer of the photosensitive composition layer, it is possible to prevent the required exposure amount from being greatly increased even when the thick film partition is formed. It becomes possible.
Moreover, it is preferable that the relationship between γ ₁ and γ ₂ satisfies the following formula (2).
6γ ₂ ≧ γ ₁ ≧ 1.5γ ₂ (2)
Furthermore, it is more preferable to satisfy | fill following formula (3).
5γ ₂ ≧ γ ₁ ≧ 2γ ₂ (3)
Further, the curing starting exposure of the curing initiator exposure amount E ₁₀ of the first photosensitive paste second photosensitive paste E ₂₀ is preferably satisfies the relation of the following formula (4).
E ₁₀ > E ₂₀ (4)
When γ ₁ is smaller than 1.5γ ₂ , the first photosensitive paste applied to the lower layer also starts to be polymerized against relatively weak scattered light, so that the pattern shape is likely to be thickened. Meanwhile, gamma ₁ is the larger than 6γ _2, there is a tendency that the exposure amount required to fully cure the first photosensitive paste applied to the lower layer is increased.

In order to increase the sensitivity characteristic value γ ₁ of the _first photosensitive paste, a method of increasing the amount of the organic component in the photosensitive paste relative to the amount of the inorganic fine particles, or a method of increasing the particle size of the inorganic fine particles In addition, it is effective to reduce the monomer content as a method for selecting and modifying the photosensitive component, but when considering the relationship with various properties, it is possible to add an ultraviolet absorber or an antioxidant. This is particularly effective because it has a small effect on the characteristics.

By adding an ultraviolet absorber to the first photosensitive paste and absorbing weak ultraviolet rays, curing at a small exposure amount can be suppressed, and γ ₁ can be increased. By using the first photosensitive paste having a large γ ₁ for the lower layer of the partition wall, pattern thickening due to scattered light can be suppressed as described above. In addition, the ultraviolet light absorber is not added to the second photosensitive paste used for the upper layer of the photosensitive composition layer, or when added, the addition amount is less than that of the first photosensitive paste, thereby reducing the photosensitive composition layer. It is possible to suppress an increase in necessary exposure amount due to absorption of exposure light in the upper layer. Further, when the second photosensitive paste is applied on the first photosensitive composition layer and dried, the ultraviolet absorber present in the first photosensitive composition layer is diffused to cause the second photosensitive composition. Since a large effect can be obtained by moving to a physical layer and forming a concentration gradient in the entire coating film, it is more preferable to increase the concentration difference of the ultraviolet absorber between the first photosensitive paste and the second photosensitive paste. Further, since the amount of the ultraviolet absorbent added to the first photosensitive paste used in the lower layer is large, pattern shape thickening due to ultraviolet reflection and scattering from the glass substrate side can be suppressed.

  The ultraviolet absorber here refers to a substance that absorbs a wavelength of 300 to 500 nm and emits the absorbed light energy as an inactive radiation (thermal energy). Usually, an ultra-high pressure mercury lamp used in photolithography technology. It is particularly effective if it has excellent absorbance at wavelengths in the vicinity of g-line (436 nm), h-line (405 nm), and i-line (365 nm), but absorbs ultraviolet rays to distinguish it from the photo-fading compound described later. This means that the total light transmittance of ultraviolet rays does not change with time.

  Specific examples include benzophenone compounds, cyanoacrylate compounds, salicylic acid compounds, benzotriazole compounds, indole compounds, inorganic fine-particle metal oxides, and the like. Among these, benzophenone compounds, cyanoacrylate compounds, benzotriazole compounds, and indole compounds are particularly effective.

  Specific examples thereof include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-. Dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2′carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octoxybenzophenone, 2- Hydroxy-4-octadecyloxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4- (2-hydroxy-3-methacryloxy) propoxybenzophenone, 2- (2'-G Roxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2 '-Hydroxy-3', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-4'-n-octoxyphenyl) benzotriazole, 2-ethylhexyl- 2-cyano-3,3-diphenyl acrylate, 2-ethyl-2-cyano-3,3-diphenyl acrylate, BONASORB UA-3901 (manufactured by Orient Chemical Co., Ltd.), BONASORB UA-3902 (indole UV absorber) Orient Chemical Co., Ltd.), BONASORB UA-3911 (Orient Chemical Co., Ltd.), SOM-2-0008 (Orient Chemical Co., Ltd.), Basic Blue, Sudan Blue, Sudan R, Sudan I, Sudan II, Sudan III, Sudan IV, Oil Orange SS, Oil Violet, Oil Yellow OB (above, Aldrich) are limited to these. Not. Furthermore, a methacryl group or the like may be introduced into the skeleton of these ultraviolet absorbers and used as a reaction type. In the present invention, one or more of these can be used.

  The addition amount of the ultraviolet absorber is preferably 0.001 to 2% by mass, more preferably 0.001 to 1% by mass in the first photosensitive paste. An ultraviolet absorber may be added to the second photosensitive paste, but it is necessary to make it less than the amount of the first photosensitive paste. By making the addition amount of the ultraviolet absorber within this range, it is possible to absorb the scattered light and suppress the pattern thickness and suppress the increase in the required exposure amount.

In the present invention, as a method for increasing the sensitivity characteristic γ ₁ of the first photosensitive paste, a method of adding a photo-fading compound can also be preferably used.

  The photochromic compound in the present invention absorbs light in the wavelength region of actinic rays when irradiated with light in the wavelength region of actinic rays and passes through changes in the chemical structure such as photolysis and photomodification, In which the absorbance in the wavelength region becomes smaller than that before irradiation. Usually, the exposure used in the photolithography technique is performed using g-line (436 nm), h-line (405 nm), and i-line (365 nm) of an ultra-high pressure mercury lamp. It is preferable that the compound also has absorption in g-line, h-line, and i-line regions.

  By adding the photo-fading compound to the first photosensitive paste, in the non-exposed part that is not exposed to the exposure light in the pattern design, the scattered light is emitted as in the case of adding the ultraviolet absorber. Absorption of the pattern shape can be suppressed. In the exposed area, the photochromic compound absorbs the energy of the exposure light and does not gradually absorb through photodecomposition or photo-denaturation, so that sufficient exposure light can easily reach the lower layer, reducing the required exposure. It is advantageous in that it can be further suppressed. Also, the photocuring contrast between the non-exposed part and the exposed part becomes clear, and the exposure amount margin can be improved.

  The photochromic compound has excellent absorbance at wavelengths near g-line, h-line, and i-line, and preferably does not absorb wavelength light near g-line, h-line, and i-line after absorption. Examples include photodegradable compounds such as a fading dye, a photoacid generator, and a photobase generator, and photomodifying compounds such as an azo dye and a photochromic compound.

  In the present invention, a photoacid generator can be particularly preferably used as the photo-fading compound. As described above, the photoacid generator can not only improve the exposure amount margin, but also, when applied to a negative photosensitive paste using an alkali-soluble resin and an aqueous alkali solution as a developer, acid is generated by exposure light. Since the acidic site of the alkali-soluble resin of the negative photosensitive paste is non-ionized, the alkali development resistance of the exposed portion can be enhanced. Examples of the photoacid generator used in the present invention include onium salts, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, sulfonimide compounds, and diazo ketone compounds.

  Specific examples of onium salts include diazonium salts, ammonium salts, iodonium salts, sulfonium salts, phosnium salts, oxonium salts, and the like. Preferred onium salts include diphenyliodonium triflate, diphenyliodonium pyrenesulfonate, diphenyl. Examples include iodonium dodecylbenzene sulfonate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalene sulfonate, (hydroxyphenyl) benzylmethylsulfonium toluenesulfonate, and the like.

  Specific examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound, a haloalkyl group-containing heterocyclic compound, and the like. Preferred halogen-containing compounds include 1,1-bis (4-chlorophenyl)- Examples include 2,2,2-trichloroethane, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine.

  Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, bis (2,4- Xylylsulfonyl-diazomethane, bis (p-chlorophenylsulfonyl-diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenyl A sulfonyl (benzoyl) diazomethane etc. can be mentioned.

  Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds, and the like, and preferable sulfone compounds include 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, and the like. Is mentioned.

  Examples of sulfonic acid ester compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, imino sulfonates, etc. Preferred sulfonic acid ester compounds include benzoin tosylate, pyrogallol trimesylate, nitro Examples include benzyl-9,10-diethoxyanthracene-2-sulfonate.

  Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoro Methylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept -5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- ( Trifluoromethylsulfonyloxy) naphthyl dicarboxylimide, N- (camphors Phonyloxy) succinimide, N- (camphorsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-di Carboxylimide, N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2. 1] Heptane-5,6-oxy-2,3-dicarboxylimide, N- (camphorsulfonyloxy) naphthyl dicarboxylimide, N- (4-methylphenylsulfonyloxy) phthalimide, N- (4-methylphenyl) Sulfonyloxy) diphenylmaleimide, N- (4-methyl) Phenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, to N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] Pto-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N -(4-methylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-trifluoromethyl) Phenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfuride) (Honyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, to N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] Pto-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide N- (2-trifluoromethylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) phthalimide, N- (4-fluorophenylsulfonyl) Oxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) bi Chlo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5 Ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (4- And fluorophenylsulfonyloxy) naphthyl dicarboxylimide.

  Specific examples of the diazoketone compound include 1,3-diketo-2-diazo compounds, benzoquinone diazide compounds, naphthoquinone diazide compounds, and the like.

  In the present invention, a naphthoquinone diazide compound is particularly preferably used as a photoacid generator from the viewpoint of heat resistance during film formation drying and low residue during baking, and specific naphthoquinone diazide compounds include 1, 2-naphthoquinone-2-diazide, 1,2-naphthoquinone-2-diazide-4-sulfonic acid sodium salt, 1,2-naphthoquinone-2-diazide-5-sulfonic acid sodium salt, 1,2-naphthoquinone-2- Diazide-4-sulfonyl chloride, 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride, 1,2-naphthoquinone-2-diazide-4-carboxylic acid, 1,2-naphthoquinone-2-diazide-5-carbon Acid, 4-nitro-1,2-naphthoquinone-2-diazide, 5-nitro-1,2-naphthoquinone-2-diazide 4-cyano-1,2-naphthoquinone-2-diazide, 5-cyano-1,2-naphthoquinone-2-diazide, 1,2-naphthoquinone-2-diazide-4-sulfonic acid and 1,2-naphthoquinone-2 -Amides of diazide-5-sulfonic acid with 2,3,4,4'-tetrahydroxybenzophenone or 1,1,1-tris (4-hydroxyphenyl) ethane, amides with diaminodiphenyl ether, etc. -Naphthoquinone-2-diazide-4-carboxylic acid or 1,2-naphthoquinone-2-diazide-5-carboxylic acid, 2,3,4,4'-tetrahydroxybenzophenone or 1,1,1-tris (4 -Hydroxyphenyl) ethane and amides with diaminodiphenyl ether and the like. Phenanthrenequinone diazide compounds are also excellent in chemical stability, and examples thereof include 9,10-phenanthrenequinone-10-diazide and derivatives thereof.

  Further, it is also preferable to use a photo-modified type fading compound such as an azo dye or a photochromic compound. It is known that azo dyes isomerize from a trans form to a cis form and change color when irradiated with ultraviolet light. The azo dye that can be used in the present invention is preferably an azobenzene derivative, and particularly preferred azobenzene derivatives include (phenylazo) phenol, hydroxyazobenzenecarboxylic acid, phenylazoaniline, dimethylaminoazobenzene, nitroazobenzene, nitrodimethylaminoazobenzene, and the like. Can be mentioned.

  Similarly, a photochromic compound is a compound that is colored or faded through photomodification upon irradiation with ultraviolet light. In the present invention, those whose ultraviolet light absorbance is reduced by irradiation with ultraviolet light are preferred, and examples include spiropyrans, spirooxazines, diarylethenes, fulgides, and cyclophanes.

  In the method for forming a partition for a flat display of the present invention, after the exposure and development steps, the organic matter is decomposed and the inorganic fine particles are sintered in the firing step to complete the pattern. Firing is generally performed at 400 to 1000 ° C., but when patterning is performed on a glass substrate, firing is performed at a temperature of 520 to 620 ° C. for 10 to 60 minutes. Accordingly, the photo-fading compound used in the present invention is preferably one that is excellent in thermal decomposability and does not inhibit the sintering of inorganic fine particles, and has a weight retention when heated from 30 ° C. to 500 ° C. at 10 ° C./min It is preferable that it is 1 mass% or less. Sintering inhibition of inorganic fine particles can be suppressed by setting the content to 1% by mass or less. In order to suppress re-foaming due to the residue during firing, the weight retention is more preferably 0.7% by mass or less.

  Moreover, after apply | coating a 1st photosensitive paste uniformly on a board | substrate, generally drying for 10 to 120 minutes at 60-150 degreeC is performed. Therefore, the photochromic compound used in the present invention is preferably excellent in thermal stability at the time of drying, and is preferably photodegraded or photomodified for the first time at the time of exposure. The temperature is increased from 30 ° C. to 100 ° C. at a rate of 10 minutes / min. It is preferable that the weight retention when maintained for 2 hours is 98% by mass or more. More preferably, it is 99 mass% or more.

  Moreover, it is preferable that the photochromic compound used in the present invention does not contain halogen such as fluorine, chlorine, bromine and iodine, sulfur element and phosphorus element in the molecule. This is because these elements are likely to be discharged as compounds harmful to the environment during firing. Further, since the combustion product of halogen is accumulated in the firing furnace, it is not preferable in terms of process management.

  As the most preferable photochromic compound having the above thermal properties, 1,2-naphthoquinone-2-diazide, 1,2-naphthoquinone-2-diazide-4-carboxylic acid, 1,2-naphthoquinone-2- Diazide-5-carboxylic acid, 1,2-naphthoquinone-2-diazide-6-carboxylic acid, 1,4-naphthoquinone-4-diazido-2-carboxylic acid, 4-nitro-1,2-naphthoquinone-2-diazide 5-nitro-1,2-naphthoquinone-2-diazide, 4-cyano-1,2-naphthoquinone-2-diazide, 5-cyano-1,2-naphthoquinone-2-diazide, 9,10-phenanthrenequinone- From a compound having a naphthoquinone diazide moiety such as 10-diazide and hydrogen, carbon, nitrogen such as hydroxyl group, carboxyl group, amino group and nitro group. Can be mentioned azobenzene derivative has undergone a substitution by a substituent.

One type of photochromic compound that can be used in the present invention may be used alone, or a mixture of two or more types may be used. The compounding ratio of the photochromic compound is preferably in the range of 0.001 to 2% by mass with respect to the first photosensitive paste, although it depends on the absorbance of the photochromic compound before exposure. If it is 0.001% by mass or less, the scattered light is not sufficiently absorbed, and the pattern shape tends to be thickened. On the other hand, when the content is 2% by mass or more, the g-line does not easily reach the lower layer, and the required exposure amount tends to increase. In order for the photochromic compound to function appropriately as a contrast enhancer, it is more preferable to blend in the range of 0.002 to 1% by mass. Moreover, it can also be added to the second photosensitive paste in a range where the sensitivity characteristic value γ ₂ is smaller than γ ₁ or less.

  The photochromic compound has the function of improving the light transmittance of the exposed portion and enhancing the contrast between the exposed portion and the non-exposed portion, but absorbs scattered light and causes structural changes such as photolysis and photo-denaturation. Thereafter, the scattered light is not absorbed. For this reason, it is preferable to add the above-described ultraviolet absorber to the first photosensitive paste of the present invention in addition to the photo-fading compound. Since the ultraviolet absorber absorbs excess scattered light, it is possible to suppress the pattern thickness and further increase the exposure amount margin.

In the present invention, an antioxidant can be added as a method for increasing γ ₁ of the first photosensitive paste. The antioxidant has a radical chain inhibiting action, a triplet elimination action, and a hydroperoxide decomposition action. When an antioxidant is added to the photosensitive paste, the antioxidant captures radicals and returns the energy state of the excited photopolymerization initiator and sensitizer to the ground state, thereby causing excess light due to scattered light. the reaction is suppressed, rapidly by photoreaction occurs in the exposure amount can not be suppressed by the antioxidant dissolved in the developer, contrast insoluble increases, it is possible to increase the gamma _1. Specifically, p-methoxyphenol, p-benzoquinone, naphthoquinone, p-xyloquinone, p-toluquinone, 2,6-dichloroquinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicaproxy-p-benzoquinone, Hydroquinone, pt-butylcatechol, 2,5-dibutylhydroquinone, mono-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, di-t-butyl-p-cresol, hydroquinone monomethyl ether, α- Naphthol, hydrazine hydrochloride, trimethylbenzylammonium chloride, trimethylbenzylammonium oxalate, phenyl-β-naphthylamine, parabenzylaminophenol, di-β-naphthylparaphenylenediamine, dinitrobenzene, trinitrobenzene, picrine Quinone dioxime, cyclohexanone oxime, pyrogallol, tannic acid, triethylamine hydrochloride, dimethylaniline hydrochloride, cuperone, 2,2'-thiobis (4-t-octylphenolate) -2-ethylhexylamino nickel- (II ), 4,4′-thiobis- (3-methyl-6-tert-butylphenol), 2,2′-methylenebis- (4-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (t -Butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,2,3-tri Examples include, but are not limited to, hydroxybenzene. In the present invention, one or more of these can be used. The addition amount of the antioxidant is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass in the photosensitive paste. By making the addition amount of the antioxidant within this range, the sensitivity of the photosensitive paste can be maintained, and the degree of polymerization can be maintained and the pattern shape can be maintained, while the contrast between the exposed portion and the non-exposed portion can be increased. . As described above, since the antioxidant can control the sensitivity characteristic value of the photosensitive paste, the antioxidant is contained only in the first photosensitive paste, so that the second on the first photosensitive composition layer. When the photosensitive paste is applied and dried, the antioxidant in the first photosensitive composition layer diffuses into the second photosensitive composition layer, and a concentration gradient can be created throughout the coating film. A great effect is achieved in achieving sensitivity and increasing the exposure margin.

  In order to satisfy the above (1) in the present invention, the first photosensitive paste and the second photosensitive paste contain a photosensitive monomer, and the content of the photosensitive monomer in the first photosensitive paste is set to be the same. It is also possible to make it less than the content of the photosensitive monomer in the second photosensitive paste.

  The photosensitive monomer is a compound containing a carbon-carbon unsaturated bond, and specific examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, isobutyl. Acrylate, tert-butyl acrylate, n-pentyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxytriethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, Glycidyl acrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl acrylate, Bonyl acrylate, 2-hydroxypropyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoro Ethyl acrylate, allylated cyclohexyl diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol Hexaax relay , Dipentaerythritol monohydroxypentaacrylate, ditrimethylolpropane tetraacrylate, glycerol diacrylate, methoxylated cyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, triglycerol diacrylate, trimethylolpropane tri Acrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, benzyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, bisphenol A diacrylate, bisphenol A-ethylene oxide adduct diacrylate, bisphenol A-propylene oxide addition Zia of things Acrylate, thiophenol acrylate, benzyl mercaptan acrylate, a monomer in which 1 to 5 hydrogen atoms of these aromatic rings are substituted with chlorine or bromine atoms, or styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, chlorinated styrene, brominated styrene, α-methylstyrene, chlorinated α-methylstyrene, brominated α-methylstyrene, chloromethylstyrene, hydroxymethylstyrene, carboxymethylstyrene, vinylnaphthalene, vinylanthracene , Vinyl carbazole, and those obtained by changing some or all of the acrylates in the molecule of the above compounds to methacrylate, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone, and the like.

  In the polyfunctional monomer containing a plurality of carbon-carbon unsaturated bonds in one molecule, the unsaturated group may be a mixture of acrylic, methacrylic, vinyl and allyl groups. In the present invention, one or more of these can be used. The addition amount of the photosensitive monomer is preferably 1 to 50% by mass in the first photosensitive paste. When the addition amount is 50% or more, the required exposure amount is significantly reduced, but the polymerization in the direction perpendicular to the light traveling direction proceeds remarkably and a pattern thicker than the exposure mask is formed. On the other hand, when the addition amount is 1% or less, the required exposure amount tends to increase and the photoreactive low molecular weight substance decreases, so that the development time tends to be delayed. By utilizing this feature, the pattern thickness can be controlled by making the addition amount of the monomer of the first photosensitive paste smaller than the addition amount of the second photosensitive paste.

  The addition of a silane coupling agent or a titanium coupling agent (hereinafter referred to as a coupling agent) to the first photosensitive paste of the present invention further increases the exposure margin when forming a high-definition pattern. preferable. From the viewpoint of ease of use and cost, a silane coupling agent is particularly preferable. A silane coupling agent is a structure in which an organic functional group having affinity or reactivity for organic substances is chemically bonded to a hydrolyzable silyl group having affinity or reactivity for inorganic materials. The titanium coupling agent has a structure in which the silane portion of the silane coupling agent is replaced with titanium. By adding a coupling agent to the paste, adhesion between a substrate containing a glass substrate and a material containing an inorganic substance and a pattern containing an organic component is improved. Usually, a pattern with a width of 60 μm or less is easily peeled off during development, but the addition of a silane coupling agent or a titanium coupling agent makes peeling during development difficult even when a high-definition pattern with a width of 50 μm or less is formed. The amount margin can be expanded.

  In the silane coupling agent, examples of the hydrolyzable group bonded to silicon include an alkoxy group, a halogen, and an acetoxy group. Usually, an alkoxy group, particularly a methoxy group and an ethoxy group are preferably used.

  Examples of the organic functional group include amino group, methacryl group, acrylic group, vinyl group, epoxy group, mercapto group, alkyl group, and allyl group. Specifically, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-aminopropyl Trimethoxysilane, γ-dibutylaminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-β- (N-vinylbenzylaminomethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-methacryloxypropyl Trimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyeth Xy) silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, n-hexyltrimethoxysilane, n-decyl Examples include trimethoxysilane, n-hexadecyltrimethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane. In the present invention, these coupling agents may be used alone or in combination of two or more. Moreover, you may use the self-condensate of one type of coupling agent, and the heterocondensate which combined 2 or more types.

  The weight average molecular weight of the coupling agent is preferably 200 to 1000, and more preferably 250 to 500. When the weight average molecular weight is 200 or more, the effect reduction due to evaporation of the coupling agent during drying of the paste coating film can be suppressed, and when it is 1000 or less, the thermal decomposability during firing is improved. Can keep.

  The organic functional group of the coupling agent is preferably a photosensitive functional group, and is preferably an ethylenically unsaturated group. Specific examples include a methacryl group, an acryl group, and a vinyl group. Coupling agents having these organic functional groups also act as monomers during photocuring of the photosensitive paste, and insolubility progresses near the boundary between the inorganic fine particles and the organic components during exposure, and the pattern meanders due to the infiltration of the developer. Can be suppressed.

  In the present invention, when a coupling agent is added to the first photosensitive paste, the first photosensitive paste is preferably heat-treated at 70 to 90 ° C. for 30 minutes to 2 hours before coating. By performing the heat treatment at 70 ° C. or higher and for 30 minutes or longer, the condensation reaction between the inorganic fine particles and the coupling agent can be dramatically accelerated, and the developing resistance of the exposed portion can be improved. In addition, since the inorganic fine particles and the coupling agent gradually react at room temperature, the viscosity of the photosensitive paste gradually increases due to the gelation mechanism. However, after the paste is prepared, heat treatment is performed to react the inorganic fine particles with the coupling agent. By proceeding to some extent, the reaction at room temperature can be suppressed, and further increase in viscosity can be prevented, and a photosensitive paste having excellent viscosity stability can be obtained. Furthermore, it can prevent that a photosensitive organic component reacts with a heat | fever by making 90 degreeC or less and heating time into 2 hours or less.

  The first photosensitive paste and the second photosensitive paste in the present invention (hereinafter, the common contents are described as the photosensitive paste of the present invention) have an organic component and inorganic fine particles as essential components, respectively, It is preferable that the glass contains low-melting glass particles.

The organic component of the photosensitive paste of the present invention is a portion obtained by removing the inorganic component from the photosensitive paste, and is preferably contained in the photosensitive paste in an amount of 5 to 50% by mass. By setting it within this range, pattern processing on a substrate by a photolithography method using a photosensitive paste containing inorganic fine particles becomes possible. In the present invention, γ ₁ can be increased by increasing the organic component content of the first photosensitive paste.
The organic component of the photosensitive paste of the present invention is composed of a photosensitive oligomer, a photosensitive polymer, in addition to the above-mentioned ultraviolet absorber, photochromic material, antioxidant, photosensitive monomer, silane coupling agent or titanium coupling agent. Additives such as photosensitive organic components, organic dyes, photopolymerization initiators, sensitizers, sensitizers, plasticizers, thickeners, dispersants, organic solvents, precipitation inhibitors selected from at least one of them It consists of adding ingredients as needed.

  As the photosensitive polymer, an alkali-soluble polymer can be preferably used. This is because when the polymer is alkali-soluble, an alkaline aqueous solution can be used as a developing solution instead of an organic solvent having a problem with the environment. As the alkali-soluble polymer, an acrylic copolymer can be preferably used. The acrylic copolymer is a copolymer containing at least an acrylic monomer as a copolymerization component. Specific examples of the acrylic monomer include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n -Butyl acrylate, sec-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxytriethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, di Cyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate 2-hydroxyethyl acrylate, isobornyl acrylate, 2-hydroxypropyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxy Acrylic monomers such as ethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, thiophenol acrylate, benzyl mercaptan acrylate, and these acrylates to methacrylate What was replaced It is. As the copolymer component other than the acrylic monomer, all compounds having a carbon-carbon double bond can be used, but preferably styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α- Examples thereof include styrenes such as methyl styrene, chloromethyl styrene, and hydroxymethyl styrene, and 1-vinyl-2-pyrrolidone.

  In order to impart alkali solubility to the acrylic copolymer, it is achieved by adding an unsaturated acid such as an unsaturated carboxylic acid as a monomer. Specific examples of the unsaturated acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetate, or acid anhydrides thereof. The acid value of the polymer is preferably in the range of 50 to 150.

  In order to improve the curing rate, it is preferable to use a photosensitive polymer in which at least a part of the polymer has a carbon-carbon double bond at a side chain or a molecular end. Examples of the group having a carbon-carbon unsaturated bond include a vinyl group, an allyl group, an acrylic group, and a methacryl group. In order to add such a functional group to a polymer, a compound having a glycidyl group or an isocyanate group and a carbon-carbon unsaturated bond with respect to a mercapto group, amino group, hydroxyl group or carboxyl group in the polymer, acrylic acid chloride, There is a method of making an addition reaction of methacrylic acid chloride or allyl chloride.

  Examples of the compound having a glycidyl group and a carbon-carbon unsaturated bond include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, glycidyl crotonate, and glycidyl isocrotonate. Examples of the compound having an isocyanate group and a carbon-carbon unsaturated bond include acryloyl isocyanate, methacryloyl isocyanate, acryloylethyl isocyanate, and methacryloylethyl isocyanate.

  As the photopolymerization initiator, a photoradical initiator that generates radicals upon irradiation with active light can be preferably used. Specific examples thereof include benzophenone, methyl o-benzoylbenzoate, and 4,4-bis (dimethylamine). Benzophenone, 4,4-bis (diethylamino) benzophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2 -Phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, Benzyl, benzildimethylketanol, benzylmethoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methylene Anthrone, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexanone, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2 -(O-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) ) Oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, Michler's ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, naphthalenesulfonyl chloride, Quinoline sulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylformine, camphorquinone, carbon tetrabrominated, tribromophenyl sulfone, benzoin peroxide And a combination of a photoreductive dye such as eosin or methylene blue and a reducing agent such as ascorbic acid or triethanolamine. In the present invention, one or more of these can be used. The photopolymerization initiator is added in an amount of 0.05 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total amount of the photosensitive monomer, the photosensitive oligomer and the photosensitive polymer. If the amount of the photopolymerization initiator is too small, the photosensitivity may be deteriorated. If the amount of the photopolymerization initiator is too large, the residual ratio of the exposed portion may be too small. Moreover, in this invention, it is possible to mix | blend so that the addition amount of a photoinitiator may differ with a 1st photosensitive paste and a 2nd photosensitive paste.

  A sensitizer can be used together with a photopolymerization initiator to improve sensitivity and to expand the effective wavelength range for the reaction. Specific examples of the sensitizer include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis ( 4-dimethylaminobenzal) -4-methylcyclohexanone, mihira-ketone, 4,4-bis (diethylamino) chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, 2- (p- Dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4-dimethylaminobenzal) acetone, 1,3-carbonylbis (4-diethylaminobenzal) acetone, 3,3-carbonylbis- (7-diethylamino) Coumarin), triethanolamine, methyldiethanol Amine, triisopropanolamine, N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl dimethylaminobenzoate , Isoamyl diethylaminobenzoate, ethyl (2-dimethylamino) benzoate, 4-dimethylaminobenzoate (n-butoxy) ethyl, 2-dimethylhexyl 4-dimethylaminobenzoate, 3-phenyl-5-benzoylthio Examples include tetrazole and 1-phenyl-5-ethoxycarbonylthiotetrazole. In the present invention, one or more of these can be used. Some sensitizers can also be used as photopolymerization initiators. When adding a sensitizer to the photosensitive paste of this invention, the addition amount becomes like this. Preferably it is 0.05-10 mass% with respect to the photosensitive organic component, More preferably, it is 0.1-10 mass%. By setting the addition amount of the sensitizer within this range, good photosensitivity can be obtained while maintaining the remaining ratio of the exposed portion.

  The photosensitive paste of the present invention can use an organic solvent in order to adjust the viscosity at the time of application according to the application method. The organic solvents used at this time are methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, bromobenzene, chlorobenzene, dibromo Benzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid and the like, and organic solvent mixtures containing one or more of these are used.

  The photosensitive paste of the present invention preferably contains low-melting glass particles having a glass transition temperature in the range of 400 to 600 ° C. as inorganic particles. This is because when the glass transition temperature is within this range, the pattern is not deformed and the melting property at the time of firing is appropriate. A more preferable range of the glass transition temperature is 430 to 550 ° C. The addition amount of the inorganic fine particles is preferably 5 to 50% by mass in the photosensitive paste.

  By using low melting point glass fine particles having such a glass transition temperature and blending metal oxide so that the refractive index of the glass fine particles is 1.5 to 1.65, an inorganic component and an organic component By matching the refractive indexes of the two and suppressing light scattering, highly accurate pattern processing becomes possible. The particle size of the low-melting glass fine particles is selected in consideration of the shape of the pattern to be produced. The 50% particle size (weight average particle size) in the weight distribution curve is 1.0 to 20 μm, and the top size is 30 μm. The following is preferable. Furthermore, it is preferable that the 10% particle diameter is 0.5 to 5 μm and the 90% particle diameter is 4 to 25 μm. More preferably, the average particle size is 1.5 to 15 μm. Within this range, light is sufficiently transmitted during exposure, and an insulating pattern with a small difference in line width between the upper and lower sides can be obtained. If the weight average particle diameter is smaller than 1.0 μm, the fine particles are too fine and light scattering tends to be intense during exposure, which is not preferable. On the other hand, when the average particle size is 20 μm or more, the top particle size becomes 30 μm or more, which is not suitable for increasing the surface roughness of the top of the partition wall or forming a high-definition partition wall.

In the present invention it is also possible to increase the gamma ₁ by increasing the weight average particle diameter of the inorganic fine particles in the first photosensitive paste. Increasing the particle size decreases the specific surface area of the inorganic fine particles, reduces scattering at the organic / inorganic interface, and increases γ ₁ in terms of improving dispersibility.

The low-melting-point glass particles that can be preferably used as the inorganic particles have, for example, the following composition in oxide notation.
Lithium oxide, sodium oxide or potassium oxide 3-15% by mass
Silicon oxide 5-30% by mass
Boron oxide 20-45 mass%
Barium oxide or strontium oxide 2-15% by mass
Aluminum oxide 10-25% by mass
Magnesium oxide or calcium oxide 2-15% by mass
As described above, at least one kind of alkali metal oxides of lithium oxide, sodium oxide, or potassium oxide is used, and the total amount is preferably 3 to 15% by mass, and more preferably 3 to 10% by mass.

  Alkali metal oxides not only facilitate the control of the glass transition temperature and thermal expansion coefficient of glass, but also can lower the refractive index of glass, thus reducing the difference in refractive index from the photosensitive organic component. Becomes easier. By making the total amount of alkali metal oxides 3% by mass or more, the effect of lowering the melting point of the glass can be obtained, and by making it 15% by mass or less, the chemical stability of the glass is maintained and the thermal expansion coefficient. Can be kept small. As the alkali metal, lithium is preferably selected in consideration of lowering the refractive index of the glass and preventing ion migration.

  The blending amount of silicon oxide is preferably 5 to 30% by mass, more preferably 10 to 30% by mass. Silicon oxide is effective in improving the denseness, strength and stability of glass, and is effective in lowering the refractive index of glass. The thermal expansion coefficient can be controlled to prevent peeling due to mismatch with the glass substrate. By setting it as 5 mass% or more, a thermal expansion coefficient is made small and it becomes difficult to produce a crack, when baking to a glass substrate. Further, the refractive index can be kept low. By setting it as 30 mass% or less, a glass transition point can be restrained low and the baking temperature to a glass substrate can be made low.

  Boron oxide is effective for lowering the refractive index, and is preferably blended in the range of 20 to 45 mass%, more preferably 20 to 40 mass%. By setting it as 20 mass% or more, the glass transition point is kept low and baking onto the glass substrate is facilitated. Moreover, the chemical stability of glass can be achieved by setting it as 45 mass% or less.

  Of these, at least one of barium oxide and strontium oxide is used, and the total amount is preferably 2 to 15% by mass, more preferably 2 to 10% by mass. These components are effective in adjusting the thermal expansion coefficient, and are also preferable in terms of ensuring electrical insulation and stability and denseness of a pattern to be formed. By setting the content to 2% by mass or more, devitrification due to crystallization can be prevented. Moreover, by setting it as 15 mass% or less, a thermal expansion coefficient and a refractive index can be restrained low, and the chemical stability of glass can be maintained.

  Aluminum oxide has the effect of expanding the vitrification range and stabilizing the glass, and is effective in extending the pot life of the paste. It is preferable to mix | blend in 10-25 mass%, By making it in this range, a glass transition point can be kept low and baking on a glass substrate can be made easy.

  Further, at least one of calcium oxide and magnesium oxide is used, and the total amount is preferably 2 to 15% by mass. These components are effective in controlling the coefficient of thermal expansion while facilitating melting of the glass. By making the total amount 2% by mass or more, devitrification of the glass due to crystallization is prevented and 15% by mass or less. Thus, the chemical stability of the glass can be maintained.

  Further, although not described in the above composition, it is also preferable to contain zinc oxide, titanium oxide, zirconium oxide or the like.

  As a method for producing the glass fine particles, for example, raw materials such as lithium oxide, silicon oxide, boron oxide, barium oxide, aluminum oxide and magnesium oxide are mixed so as to have a predetermined composition, and melted at 900 to 1200 ° C. It is cooled and made into a glass frit and then pulverized into fine particles of 1 to 5 μm. High purity carbonates, oxides, hydroxides and the like can be used as raw materials. Depending on the type and composition of the fine glass particles, the use of ultra-high purity alkoxide of 99.99% or more and organic metal raw materials, and the use of glass fine particles that are homogeneously produced by the sol-gel method, provide a high electric resistance and high density. This is preferable because a high-purity insulating layer with few pores can be obtained.

  Moreover, it is preferable to contain a filler component in addition to the low softening point glass fine particles as the inorganic fine particles of the photosensitive paste. The filler component in the present invention refers to inorganic fine particles which are added to improve pattern strength and firing shrinkage rate and hardly melt and flow even at firing temperatures. By adding a filler component, the shrinkage | contraction by baking of a pattern can be suppressed or the intensity | strength of a pattern can be improved. As the filler component, those having an average particle diameter of 1 to 4 μm and an average refractive index of 1.4 to 1.7 are preferably used in consideration of dispersibility and filling properties in the photosensitive paste and suppression of light scattering during exposure. can do. In the present invention, as such a filler component, at least one selected from high melting point glass fine particles having a refractive index adjusted and ceramic fine particles such as cordierite, alumina, silica, magnesia, zirconia, and the like can be used. However, from the viewpoint of easy adjustment of the average particle diameter and average refractive index, it is preferable to use high melting point glass fine particles.

  As the high melting point glass fine particles, those having a glass transition temperature of 500 to 1200 ° C. are preferably added in a composition range of 3 to 40 mass% with respect to the total inorganic fine particles. When the amount is less than 3% by mass, the edge of the pattern tends to collapse during firing, and it tends to be difficult to obtain a pattern with a good shape. On the other hand, when it is more than 40% by mass, the denseness of the pattern to be formed is lowered, which is not preferable.

  It is also a preferred practical form of the present invention to use inorganic fine particles that have been surface-treated with the above coupling agent or titanium coupling agent. By using the inorganic fine particles subjected to the surface treatment, the affinity between the inorganic fine particles and the organic component can be increased, and the development resistance of the exposed portion can be improved. The surface treatment method is arbitrary. For example, an aqueous solution method in which a dilute aqueous solution containing a coupling agent is prepared to impregnate inorganic fine particles, an organic solvent method in which an organic solvent containing a coupling agent is applied, a direct coupling agent The spray method etc. which spray can be mentioned.

  The photosensitive paste of the present invention has a predetermined composition of components such as a photo-fading compound, an ultraviolet absorber, a silane coupling agent, an antioxidant, inorganic fine particles, a photosensitive organic component, an organic dye, a dispersant, and a solvent. It is preferable to carry out the main kneading after pre-kneading after blending so that. The preliminary mixing can be preferably applied by hand stirring, a magnetic stirrer, or a mechanical stirrer. Further, when adding a photosensitive polymer, it may be added directly to the dispersion, but adding a photosensitive polymer solution in which a photosensitive polymer is dissolved in advance in an organic solvent provides a uniform photosensitive paste. This is preferable. Next, main kneading is performed using a kneading apparatus such as a three-roller, and the mixture is uniformly dispersed to produce a glass paste. It is also preferable to filter the glass paste after the main kneading using a filter having an opening of 1 to 20 μm. Furthermore, it is also preferable to defoam the glass paste using a kneading / degassing machine or a vacuum stirrer.

  A partition for a flat display is formed using the photosensitive paste of the present invention thus obtained.

  In the present invention, the first photosensitive paste and the second photosensitive paste satisfying the above-described formula (1) are used, and the first photosensitive paste is applied onto at least a glass substrate and dried. Forming a photosensitive composition layer, applying a second photosensitive paste on the first photosensitive composition layer and drying to form a second photosensitive composition layer, first photosensitive composition It is the formation method of the partition for flat displays which includes the process of exposing simultaneously a physical layer and a 2nd photosensitive composition layer, developing and forming a pattern, and the process of baking the obtained pattern in the said order.

  As the glass substrate of the present invention, “PD200” manufactured by Asahi Glass or “PP8” manufactured by Nippon Electric Glass, which is a heat-resistant glass, can be used in addition to soda glass.

  When used as a member for a plasma display, an electrode pattern is formed on a glass substrate with a metal such as silver, aluminum, chromium or nickel. As a method for forming an electrode, a metal paste mainly composed of these metal fine particles and an organic binder is subjected to pattern printing and baking by screen printing, or a photosensitive metal paste using a photosensitive organic component as an organic binder. After coating, a photosensitive paste method can be used in which pattern exposure is performed using a photomask, unnecessary portions are dissolved and removed in a development step, and further, heated and baked at 350 to 600 ° C. to form an electrode pattern. . Further, an etching method can be used in which after chromium or aluminum is vapor-deposited on a glass substrate, a resist is applied, and after the resist is subjected to pattern exposure and development, unnecessary portions are removed by etching.

  When used as a member for a plasma display, it is preferable to provide a dielectric layer after electrode formation. By providing the dielectric layer, it is possible to improve the stability of discharge and to prevent the partition wall formed on the upper layer of the dielectric layer from falling or peeling off. As a method of forming the dielectric layer, a dielectric paste mainly composed of inorganic fine particles such as glass and high-melting glass fine particles and an organic binder is applied on the entire surface with a screen printer, a slit die coater, or a release film. There is a method in which a front surface is printed or coated and then transferred onto a substrate on which an electrode is formed.

  Next, a method for forming partition walls by photolithography will be described. The partition pattern is not particularly limited, but a lattice shape, a waffle shape, a via hole shape, and the like are preferable.

  In the present invention, a partition paste made of a first photosensitive paste is applied on a substrate on which an electrode or a dielectric is formed. For coating, an apparatus such as a bar coater, a roll coater, a slit die coater, a blade coater, or a screen printing machine can be used. The coating thickness can be determined in consideration of the desired partition wall height and the shrinkage rate due to baking of the paste. The coating thickness can be adjusted by the number of coatings, screen mesh, paste viscosity, and the like. For field emission displays and fluorescent display tubes, the thickness after firing is preferably 5 to 50 μm, and for plasma displays, it is preferably applied to 50 to 200 μm.

  In the present invention, after the step of forming the first photosensitive composition layer and before the step of forming the second photosensitive composition layer, the first photosensitive composition layer is exposed, A partition wall having a stepped structure can be formed. In general, the exposure is performed through a photomask so as to be performed by ordinary photolithography. The photomask used for exposure to the first photosensitive composition layer and the first photosensitive composition layer By changing the shape of the photomask used when the second photosensitive composition layer is exposed simultaneously, a partition wall having a stepped structure can be obtained. In the case of forming a grid-shaped cross-girder partition having a structure in which the unidirectional main partition is higher than the other auxiliary partition, for example, a stripe mask for the auxiliary partition for the first photosensitive composition layer. The second photosensitive composition layer is formed on the first photosensitive composition layer and then exposed using a stripe mask for the main partition perpendicular to the auxiliary partition stripe mask. It is valid. Thus, even if it exposes several times, by using the formation method of the present invention, the first photosensitive composition layer and the second photosensitive composition layer are simultaneously exposed in the subsequent exposure process. This is effective for suppressing pattern thickening at the bottom of the portion to be formed. Alternatively, a method of directly drawing with a laser beam or the like without using a photomask may be used.

As the exposure apparatus, a stepper exposure machine, a proximity exposure machine, or the like can be used. Moreover, when performing exposure of a large area, a large area can be exposed with an exposure machine having a small exposure area by applying a photosensitive paste on a substrate such as a glass substrate and then performing exposure while transporting. it can. Examples of the active light source used at this time include near ultraviolet rays, ultraviolet rays, electron beams, X-rays, and laser beams. Among these, ultraviolet rays are most preferable, and as the light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a halogen lamp, or a germicidal lamp can be used. Among these, an ultrahigh pressure mercury lamp is suitable. Although exposure conditions vary depending on the coating thickness, exposure is usually performed for 0.01 to 30 minutes using an ultrahigh pressure mercury lamp having an output of 1 to 100 mW / cm ² .

  In the present invention, after the first photosensitive paste is applied and dried, a second photosensitive paste having a sensitivity characteristic value γ smaller than that of the first photosensitive paste is applied and dried. The coating thickness can be adjusted according to the barrier rib structure and desired sensitivity, but it is preferable that the coating thickness is 5 to 50 μm for a field emission display and a fluorescent display tube, and 5 to 200 μm for a plasma display.

  After drying, exposure is performed using a photomask that determines the final partition wall shape. A striped mask is used to form a stepped partition wall.

  In the present invention, after the second photosensitive paste is applied and dried, the third photosensitive paste is further applied and dried, and exposure and development can be performed collectively.

  After the exposure, development is performed by utilizing the difference in solubility between the exposed portion and the non-exposed portion in the developer. Usually, the immersion method, the spray method, the brush method, and the like are performed. As the developer, an organic solvent in which an organic component in the photosensitive paste can be dissolved can be used. However, when a compound having an acidic group such as a carboxyl group is present in the photosensitive paste, development can be performed with an alkaline aqueous solution. As the alkaline aqueous solution, sodium hydroxide, sodium carbonate, potassium hydroxide aqueous solution or the like can be used. However, it is preferable to use an organic alkaline aqueous solution because an alkaline component can be easily removed during firing.

  As the organic alkali, a general amine compound can be used. Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, and diethanolamine.

The density | concentration of aqueous alkali solution is 0.05-5 mass% normally, More preferably, it is 0.1-1 mass%. If the alkali concentration is too low, it is difficult to remove the soluble part, and if the alkali concentration is too high, the pattern may be peeled off or corroded, which is not preferable. The development temperature during development is preferably 20 to 50 ° C. in terms of process control.
Next, firing is performed in a firing furnace. The firing atmosphere and temperature vary depending on the type of paste and substrate, but firing is performed in air, in an atmosphere of nitrogen, hydrogen, or the like. As the firing furnace, a batch-type firing furnace or a roller conveyance type continuous firing furnace can be used. The baking temperature is preferably a temperature at which the resin to be used sufficiently debinds. Usually, when an acrylic resin is used, baking is performed at 430 to 650 ° C. If the firing temperature is too low, the resin component tends to remain, and if it is too high, the glass substrate may be distorted and cracked. Through the above process, the partition for a flat display of the present invention is formed.

  Next, a method for manufacturing a display using this partition will be described.

In the case of forming a back plate for a plasma display, after forming electrodes, dielectrics and barrier ribs on a glass substrate, a phosphor is formed between the barrier ribs using a phosphor paste. It can be formed by a photolithography method using a photosensitive phosphor paste, a dispenser method, a screen printing method, or the like. The thickness of the phosphor is not particularly limited, but is 0.01 to 0.03 mm, more preferably 0.015 to 0.025 mm. The phosphor fine particles are not particularly limited, but the following phosphors are preferable from the viewpoints of light emission intensity, chromaticity, color balance, lifetime, and the like. Blue is an aluminate phosphor (for example, BaMgAl ₁₀ O ₁₇ : Eu) or CaMgSi ₂ O ₆ activated with divalent europium. In the case of green, Zn ₂ SiO ₄ : Mn, YBO ₃ : Tb, BaMg ₂ Al ₁₄ O ₂₄ : Eu, Mn, BaAl ₁₂ O ₁₉ : Mn, and BaMgAl ₁₄ O ₂₃ : Mn are preferable in terms of panel luminance. More preferably _Zn 2 _SiO 4: is Mn. In red, (Y, Gd) BO ₃ : Eu, Y ₂ O ₃ : Eu, YPVO: Eu, and YVO ₄ : Eu are also preferable. More preferred is (Y, Gd) BO ₃ : Eu.

  Next, a method for producing a front plate for plasma display will be described. As the substrate, in addition to soda glass, “PP8” (manufactured by Nippon Electric Glass Co., Ltd.) or “PD200” (manufactured by Asahi Glass Co., Ltd.), which is a heat resistant glass for plasma display, can be used. The size of the glass substrate is not particularly limited, and a glass substrate having a thickness of 1 to 5 mm can be used.

  First, indium-tin oxide (ITO) is sputtered on a glass substrate, and a pattern is formed by a photoetching method. Subsequently, the black electrode paste for black electrodes is printed. The black electrode paste is composed mainly of an organic binder, a black pigment, conductive fine particles, and a photosensitive component when used in a photolithography method. As the black pigment, a metal oxide is preferably used. Examples of metal oxides include titanium black, copper, iron, manganese oxides and their composite oxides, and cobalt oxides. Cobalt oxides are less susceptible to fading when mixed with glass and fired. Is excellent. Examples of the conductive fine particles include metal fine particles and metal oxide fine particles. As the metal fine particles, gold, silver, copper, nickel or the like that is usually used as an electrode material can be used without any particular limitation. Since this black electrode has a high resistivity, an electrode paste having a high conductivity (for example, a material containing silver as a main component) is printed on the black electrode paste in order to produce a bus electrode by producing an electrode with a low resistivity. Print on the side. As this conductive paste, an electrode paste used for an address electrode can also be suitably used. Then, batch exposure / development is performed to produce a bus electrode pattern. In order to ensure the conductivity, a highly conductive electrode paste may be printed again before development, and may be collectively developed after re-exposure. After the bus electrode pattern is formed, baking is performed. Thereafter, it is preferable to form a black stripe or a black matrix in order to improve contrast. Next, a transparent dielectric layer is formed using a transparent dielectric paste. The transparent dielectric paste is mainly composed of an organic binder, an organic solvent, and glass, but an additive such as a plasticizer may be appropriately added. The method for forming the transparent dielectric layer is not particularly limited. For example, the transparent dielectric paste is applied to the entire surface of the substrate on which the electrode is formed by screen printing, bar coater, roll coater, die coater, blade coater, spin coater, etc. Or after apply | coating partially, it can dry using arbitrary things, such as ventilation oven, a hotplate, an infrared drying furnace, and vacuum drying, and a thick film can be formed. It is also possible to make the transparent dielectric paste into a green sheet and laminate it on the electrode forming substrate. The thickness is preferably 0.01 to 0.03 mm.

  Next, firing is performed in a firing furnace. The firing atmosphere and temperature vary depending on the type of paste and substrate, but firing is performed in air, in an atmosphere of nitrogen, hydrogen, or the like. As the firing furnace, a batch-type firing furnace or a roller conveyance type continuous firing furnace can be used. The baking temperature is preferably a temperature at which the resin to be used sufficiently debinds. Usually, when an acrylic resin is used, baking is performed at 430 to 650 ° C. If the firing temperature is too low, the resin component tends to remain, and if it is too high, the glass substrate may be distorted and cracked.

Further, a protective film is formed. As the protective film, MgO, MgGd ₂ O ₄ , BaGd ₂ O ₄ , Sr _0.6 Ca _0.4 Gd ₂ O ₄ , Ba _0.6 Sr _0.4 Gd ₂ O ₄ , SiO ₂ , TiO ₂ , Al ₂ O ₃ and at least one kind from the above-mentioned group of low softening point glasses are preferably used, and MgO is particularly preferable. As a method for producing the protective film, a known technique such as electron beam evaporation or ion plating is suitable.

  Next, a method for manufacturing a plasma display panel will be described. After sealing the back substrate and the front substrate of the present invention, the space formed between the two substrates is evacuated while heating, and then a discharge composed of He, Ne, Xe, etc. is enclosed. Seal. From the viewpoint of both discharge voltage and luminance, a Xe-Ne mixed gas having .Xe of 5 to 15% by volume is preferable. In order to increase the generation efficiency of ultraviolet rays, Xe may be further increased to about 30% by volume.

  Finally, a plasma display panel can be manufactured by mounting and aging the drive circuit.

  When manufacturing a cathode substrate for field emission display using the partition wall forming method of the present invention, after forming electrodes and partition walls on a glass substrate, after depositing nickel or aluminum, a resist is applied, and the resist is subjected to pattern exposure / After development, unnecessary portions are removed by etching, and a gate electrode is formed on the partition wall. Next, an electrode pattern is formed on the gate electrode with a metal such as silver, aluminum, chromium, or nickel. As a method of forming, after applying a metal paste mainly composed of these metal fine particles and an organic binder by screen printing, or after applying a photosensitive metal paste using a photosensitive organic component as an organic binder, It is possible to use a photosensitive paste method in which pattern exposure is performed using a photomask, unnecessary portions are dissolved and removed in a development step, and further heated and baked at 350 to 600 ° C. to form an electrode pattern. Further, an etching method can be used in which after silver or aluminum is vapor-deposited on a glass substrate, a resist is applied, an unnecessary portion is removed by etching after pattern exposure / development of the resist. After the electrodes are formed, the cathode substrate can be formed by forming an emitter between the partition walls by a rotary evaporation method or CNT paste.

  Next, a method for producing an anode substrate for a field emission display will be described. First, indium-tin oxide (ITO) is sputtered on a glass substrate, and a pattern is formed by a photoetching method. Next, a black resin paste for black matrix (BM) is printed. The black resin paste contains an organic binder, a black pigment, and a photosensitive component as a main component when used in a photolithography method. As the black pigment, carbon black or metal oxide is preferably used. Examples of the metal oxide include titanium black, copper, iron, manganese oxides, composite oxides thereof, and cobalt oxides. Next, a phosphor layer is formed on the transparent electrode. The phosphor layer can be formed by a photolithography method using a photosensitive phosphor paste, a dispenser method, a screen printing method, or the like. Next, an aluminum back film is formed by vapor deposition, and an anode substrate can be formed by disposing a spacer.

  Next, a method for manufacturing a field emission display will be described. After sealing the cathode substrate and the anode substrate of the present invention, the space formed between the two substrates is evacuated while being heated and then sealed. Finally, a field emission display can be manufactured by attaching a drive circuit and aging.

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to this.

A. Thermogravimetric measurement of photochromic compound and silane coupling agent The weight retention of the photochromic compound at 500 ° C. was measured using a thermogravimetric measuring device (“TGA-50” manufactured by Shimadzu Corporation, manufactured by Shimadzu Corporation). Then, the temperature was increased from 30 ° C. to 500 ° C. at 10 ° C./min in an air atmosphere (flow rate 20 ml / min), and the calculation was performed using the formula of (weight at 500 ° C.) / (Weight at 30 ° C.) × 100. . The weight retention when the photo-fading compound and the silane coupling agent were held at 100 ° C. for 2 hours was 30 at 10 ° C./min under the air atmosphere (flow rate 20 ml / min) using the same thermogravimetric measuring device. The temperature was raised from 100 ° C. to 100 ° C., held at 100 ° C. for 2 hours, and calculated by the following formula: (weight after holding at 100 ° C. for 2 hours) / (weight at 30 ° C.) × 100. The weight retention of the photo-fading compound and the silane coupling agent when held at 100 ° C. for 2 hours is the same as the thermogravimetric measurement device. 20 mg of the photochromic compound was weighed in the cell, and using a thermogravimetric apparatus (“TGA-50” manufactured by Shimadzu Corp., manufactured by Shimadzu Corp.) under an air atmosphere (flow rate 20 ml / min), 10 ° C./min. The temperature was raised from 30 ° C. to 500 ° C., and the calculation was performed according to the formula of (weight at 500 ° C.) / (Weight at 30 ° C.) × 100.

B. Production of photosensitive paste The photosensitive paste was produced in the following manner.

  After weighing a predetermined amount of photosensitive monomer, photosensitive polymer, photopolymerization initiator, sensitizer, antioxidant, photo-fading compound, ultraviolet absorber and silane coupling agent, γ-butyrolactone is added as a solvent as appropriate. The viscosity was adjusted, inorganic particles composed of glass fine particles / filler = 80/20 (mass ratio) were added, and the mixture was kneaded with a three-roller kneader to obtain a negative photosensitive paste. The compositions of the photosensitive paste excluding the solvent are shown in Tables 1 to 3.

The raw materials used for the photosensitive paste are as follows.
Photosensitive monomer 1: Trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd.)
Photosensitive monomer 2: Tetrapropylene glycol dimethacrylate (manufactured by NOF Corporation)
Photosensitive polymer: a product obtained by adding 0.4 equivalent of glycidyl methacrylate to a carboxyl group of a copolymer of methacrylic acid / methyl methacrylate / styrene = 40/40/30 (weight average molecular weight 43,000, acid value) 100)
Photopolymerization initiator: IC369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, manufactured by Ciba Specialty Chemicals)
Sensitizer: 2,4-diethylthioxanthone antioxidant: 1,6-hexanediol-bis [(3,5-di-t-butyl-4-hydroxyphenyl) propionate])
Photochromic compound 1: 1,2-naphthoquinone-2-diazide-4-sulfonic acid sodium salt (manufactured by Wako Pure Chemical Industries, Ltd., absorption maximum wavelength; 355 nm and 400 nm, weight retention at 500 ° C .; 0.3 mass) %, Weight retention when held at 100 ° C. for 2 hours; 99.8%)
UV absorber 1: Sudan IV (Tokyo Ohka Kogyo Co., Ltd., absorption wavelength: 350 nm and 520 nm)
Silane coupling agent 1: γ-methacryloxypropyltriethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903 weight average molecular weight; 246, weight retention when held at 100 ° C. for 2 hours; 91%)
Inorganic fine particles:
Low melting point glass fine particles 1: lithium oxide 7% by mass, silicon oxide 22% by mass, boron oxide 33% by mass, zinc oxide 3% by mass, aluminum oxide 19% by mass, magnesium oxide 6% by mass, barium oxide 5% by mass, calcium oxide Low melting point glass fine particles consisting of 5% by mass. Glass transition temperature 491 ° C., average particle size 4 μm.
Low melting glass fine particles 2: Low melting glass fine particles having the same composition as the low melting glass fine particles 1. Average particle size 8 μm.
Filler: refractory glass fine particles having the following composition. Sodium oxide 1% by mass, silicon oxide 40% by mass, boron oxide 10% by mass, aluminum oxide 33% by mass, zinc oxide 4% by mass, calcium oxide 9% by mass, titanium oxide 3% by mass (glass transition temperature: 652 ° C.)
C. Preparation of electrode paste The electrode paste is composed of the photosensitive polymer (7% by mass), the photosensitive monomer 1 (3% by mass), the photopolymerization initiator (1% by mass), and the urethane compound UA-5348PE (1% by mass). And dipropylene glycol monomethyl ether (5% by mass) are dissolved while heating to 50 ° C., and then silver fine particles (average particle size 1.5 μm, specific surface area 0.80 m ² / g, 70% by mass) are added, It was prepared by kneading using a kneader.

D. Preparation of Dielectric Paste Dielectric paste is composed of polymer solution: ethyl cellulose (number average molecular weight 80000) 5% by mass terpineol solution (20% by mass), photosensitive monomer 1 (10% by mass), polymerization initiator (1,1- Azobiscyclohexane-1-carbonitrile (5% by mass) and urethane compound (5% by mass) are dissolved while heating to 50 ° C., and inorganic components (low melting point glass powder: 38% by mass of bismuth oxide, 6% by mass of silicon oxide) %, Boron oxide 20 mass%, zinc oxide 20 mass%, aluminum oxide mass 4%, glass transition point 475 ° C., softening point 515 ° C., thermal expansion coefficient 75 × 10 ⁻⁷ / ° C., density 4.61 g / cm ³ ) (40% by mass), filler (silicon oxide: manufactured by Nippon Aerosil Co., Ltd., “Aerosil 200” 5% by mass), conductor powder (titanium oxide, 10% by mass), TE A mixture composed of lupineol (5% by mass) was prepared by kneading with a three-roller kneader. In addition, the titanium oxide mixed as conductive powder also has a role as a filler component.

E. Evaluation of sensitivity characteristic value γ _n An evaluation sample was prepared according to the following procedure. First, a dielectric paste was applied on a glass substrate by a screen printing method and dried at 160 ° C. to form a 10 μm dielectric layer. Next, a photosensitive paste was applied onto the dielectric layer by multiple application / drying by screen printing so that the thickness was 50 μm after drying. Intermediate drying was performed at 100 ° C. for 5 minutes, and finally dried at 100 ° C. for 20 minutes. Exposure from 10 mJ / cm ² by an ultra-high pressure mercury lamp with an output of 50 mW / cm ² to 500 mJ / cm ^2, was subjected to ultraviolet exposure by changing the exposure condition to 10 mJ / cm ² intervals. Thereafter, a development time was obtained by developing a 0.3 mass% monoethanolamine 0.3 mass% aqueous solution at 35 ° C. in a shower as a development time, washed with water using a shower spray, and used as a sample after drying. The cross section of the remaining film portion was cut, and the remaining film thickness was measured using an optical microscope (NiKON, OPTIPHOT300). A characteristic log graph was created by plotting the common logarithm of the exposure amount on the horizontal axis and the residual film ratio on the vertical axis. Among these characteristic curves, an approximate straight line is obtained from the data in the range of the remaining film ratio of 20 to 80% by the least square approximation method. The horizontal axis intercept of the approximate straight line is read as logE _n0 . Further, the exposure amount at which the _remaining film ratio was 100% was read from the graph as _En 100, and the linear gradient γ _n was calculated as γ _n = 1 / (logE _n100 -logE _n0 ).

D. Creating evaluation sample for evaluation center exposure E _c and exposure margin was performed by the following procedure. First, a dielectric paste was applied on a glass substrate by a screen printing method and dried at 160 ° C. to form a 10 μm dielectric layer. Next, the 1st photosensitive paste was apply | coated so that it might become a thickness of 100 micrometers after drying by multiple application | coating / drying by a screen printing method. Intermediate drying was performed at 100 ° C. for 10 minutes. Next, exposure was performed through an exposure mask. The exposure mask has a pitch of 700 μm, a line width of 40 μm, and a negative type designed so that a stripe-shaped auxiliary barrier rib pattern can be formed with the horizontal direction as the longitudinal direction when the direction of the short side of the display area is the vertical direction. Chrome mask. In the exposure, 250 mJ / cm ^{2 was} irradiated with an ultrahigh pressure mercury lamp having an output of 50 mW / cm ² . Next, the 2nd photosensitive paste was apply | coated so that it might become the thickness of 50 micrometers after drying by multiple application | coating / drying by the screen printing method on the 1st photosensitive composition layer. Intermediate drying was performed at 100 ° C. for 10 minutes. Next pitch 300 [mu] m, line width 40 [mu] m, the vertical direction using a stripe-shaped main barrier rib exposure mask whose longitudinal direction, from 50 mJ / cm ² to 500 mJ / cm ^2, were UV exposure to 50 mJ / cm ² every . Thereafter, a 0.3 mass% aqueous solution of monoethanolamine was developed by applying it for 150 seconds in a shower, and was washed with water using a shower spray to remove the uncured space portion. Furthermore, it hold | maintained at 560 degreeC for 30 minutes, and baked to make the sample. The panel prepared at each exposure amount is divided into five to form small substrates, and one point is randomly selected on each small substrate, and a cross section perpendicular to the longitudinal direction of the main partition is observed with a scanning electron microscope (Hitachi, S2400). and measures a bottom width L _b of the partition wall, and the average value was calculated.
The minimum exposure amount satisfying 40 ≦ L _b ≦ 55 (μm) is E _l (mJ / cm ² ), the maximum exposure amount is E _t (mJ / cm ² ), and the center exposure amount E _c is (E _l + E _t ). / 2 (mJ / cm ² ). At this time, as shown by calculating the exposure margin _{(E t -E c) / E} c × 100 (%). E _c indicates that more needs a small exposure amount smaller, preferably 200 mJ / cm ² or less in consideration of the tact in production. Further, in order to stably produce a high-definition plasma display that is free from lighting and flicker with a 42-inch or larger plasma display, the exposure margin is preferably 15% or more.

H. Display Manufacturing Method First, a plasma display front plate was prepared by the following procedure. An ITO electrode having a thickness of 1 μm was formed on a “PD-200” glass substrate (42 inches) manufactured by Asahi Glass Co., Ltd. by a photoetching method, and then a bus electrode pattern was formed by a photolithography method using a photosensitive silver paste. . Thereafter, a transparent dielectric layer was formed to a thickness of 30 μm by screen printing. Finally, a 500 nm thick MgO film was formed by electron beam evaporation to obtain a front plate.

The plasma display back plate was prepared by the following procedure. On an “PD-200” glass substrate (42 inches) manufactured by Asahi Glass Co., Ltd., an electrode paste was used to form a coating film having a thickness of 8 μm by a screen printing method, and then an address electrode pattern was formed by a photolithography method. Next, a dielectric layer having a thickness of 20 μm was formed on the glass substrate on which the address electrodes were formed by a screen printing method. After that, the first photosensitive paste is repeatedly applied and dried several times or more on the back plate glass substrate on which the address electrode pattern and the dielectric layer are formed by screen printing so that the thickness after drying becomes 100 μm. did. Drying during printing was performed at 100 ° C. for 10 minutes. Next, exposure was performed through an exposure mask. The exposure mask is a negative chrome mask designed to enable the formation of a stripe-shaped auxiliary barrier rib pattern in a plasma display with a pitch of 700 μm and a line width of 40 μm. In the exposure, 250 mJ / cm ^{2 was} irradiated with an ultrahigh pressure mercury lamp having an output of 50 mW / cm ² . Next, the second photosensitive paste was printed several times by screen printing so that the thickness after drying was 150 μm including the lower layer. Drying during printing was performed at 100 ° C. for 10 minutes. A negative chrome mask having a pitch of 300 μm and a line width of 40 μm was used as an exposure mask, and ultraviolet exposure was performed from the top surface with an ultrahigh pressure mercury lamp having an output of 50 mW / cm ² . The exposure amount was E _c (mJ / cm ² ) determined above.

  Next, a 0.3% by mass aqueous solution of monoethanolamine kept at 35 ° C. was developed by applying it for 150 seconds in a shower, and was washed with water using a shower spray to remove the uncured space portion. Furthermore, the partition was formed by hold | maintaining for 30 minutes and baking at 560 degreeC. Next, a phosphor layer was formed to a thickness of 20 μm by a dispenser method and fired to obtain a back plate.

  After sealing the produced front plate and back plate, a noble gas of xenon-neon mixed gas of 5% by volume of xenon is sealed in a space formed between the front and back substrates at a pressure of 450 mmHg, thereby plasma display A panel portion was prepared. Further, a plasma display was manufactured by mounting a driver IC for driving.

I. Evaluation method of display characteristics The panels were turned on every other row along the partition wall direction, and visually evaluated for lighting, non-lighting, or flickering due to erroneous discharge. The evaluation is that the display characteristics are AA if the number of lit cells or non-lighted cells due to erroneous discharge is 1 or less, and the display characteristics are A if 2-4, and unsuitable as a display if 5-7. Yes, B, 8 or more, not possible as a display panel, and C.

Example 1
Table 4 shows the results when the photosensitive paste containing the photo-fading compound was used only for the first photosensitive paste. The photochromic compound 1 had a naphthoquinone diazide moiety in the molecule, was excellent in photochromic properties in the g-line region, and had a large exposure dose margin. When γ ₁ is increased, the amount of central exposure compared to Comparative Example 1 in which the first photosensitive paste of Example 1 was used for both the first photosensitive composition layer and the second photosensitive composition layer. E _c is reduced, exposure margin expanded. In the display evaluation characteristics, no erroneous lighting of the panel was observed.

(Example 2)
Table 4 shows the results when the second photosensitive paste also contains a photo-fading compound and the content thereof is less than the content in the first photosensitive paste. Compared to Example 1, both the central exposure amount E _c and the exposure margin were slightly inferior, but both were acceptable. The display evaluation characteristics were also good.

(Example 3)
Table 4 shows the results when using a photosensitive paste containing an ultraviolet absorber only in the first photosensitive paste. Although both the central exposure amount E _c and the exposure margin are slightly inferior to those of the first embodiment, both the E _c and the exposure amount margin are increased compared to the comparative example 2 which is a uniform layer. The display evaluation characteristics were also good.
Example 4
Table 4 shows the results when the photosensitive paste containing the photo-fading compound and the ultraviolet absorber was used only for the first photosensitive paste. By combining the light fade compound and an ultraviolet absorber, although the center exposure E _c compared with Example 1 increased slightly, the amount of exposure margin can be greatly expanded, also observed erroneous lighting of the panel It was.

(Example 5)
Table 4 shows the results when a photosensitive paste containing an antioxidant and an ultraviolet absorber was used only for the first photosensitive paste. By combining the antioxidant and the ultraviolet absorber, the center exposure E _c is increased but was acceptable. On the other hand, the exposure amount margin could be greatly increased, and no erroneous lighting of the panel was observed.

(Example 6)
Table 4 shows the results when the photosensitive monomer content of the first photosensitive paste was less than the second photosensitive paste content. The γ value can be controlled by adjusting the monomer amount, and both the central exposure amount E _c and the exposure amount margin are improved. However, the dissolution time of the unexposed area increased 1.5 times. The display evaluation characteristics were also good.

(Example 7)
Table 4 shows the results when the average particle size of the low softening point glass of the first photosensitive paste was 8 μm and formulated. Dispersible by increasing the glass particle size is increased, with improved gamma _1. Both the central exposure amount E _c and the exposure amount margin were improved. Although the roughness of the side wall of the partition wall increased, the display characteristics were not particularly affected and were good.

(Example 8)
Table 4 shows the results obtained when the organic component content of the first photosensitive paste was made larger than the second photosensitive paste content and prepared. Dispersible by increasing the organic component is increased, and increased gamma ₁ is. Both the central exposure amount E _c and the exposure amount margin were acceptable. Increasing the organic component increased the amount of binder removed during firing, but the display characteristics were not particularly affected and were good.

Example 9
The results of adding the silane coupling agent to the composition of Example 4 are shown in Table 4. The addition of the silane coupling agent, compared E _c is further improved in Example 4.

(Comparative Example 1)
Table 4 shows the results when the photosensitive paste having the same composition containing the photo-fading compound was used as the first photosensitive paste and the second photosensitive paste. By containing the light fade compound, exposure margin expanded significantly, although the results erroneous lighting of the panel was not, were those central exposure E _c is greatly inferior.

(Comparative Example 2)
Table 4 shows the results when a paste containing an ultraviolet absorber together with the first photosensitive paste and the second photosensitive paste and having a uniform content as a whole coating film was used. When the ultraviolet absorber was included, the central exposure amount was not changed as compared with Comparative Example 1, but the exposure amount margin was narrowed. As a result, display characteristics were not possible.

(Comparative Example 3)
Table 4 shows the results when the photosensitive paste containing the photo-fading compound was used only for the second photosensitive paste. Compared with Example 1, the central exposure amount was not changed, but the exposure amount margin was remarkably narrowed. As a result, display characteristics were not possible.

Claims (7)

Applying and drying a first photosensitive paste on at least a glass substrate to form a first photosensitive composition layer, applying and drying a second photosensitive paste on the first photosensitive composition layer Forming a second photosensitive composition layer, simultaneously exposing and developing the first photosensitive composition layer and the second photosensitive composition layer to form a pattern, and the resulting pattern In this order, the sensitivity characteristic value γ ₁ of the first photosensitive paste and the sensitivity characteristic value γ ₂ of the second photosensitive paste are expressed by the following formula ( A method for forming a partition for a flat display, which satisfies 1).
γ ₁ > γ ₂ (1)
Here, gamma _{n (n} is 1 or 2) is applied to the photosensitive paste, to the coating of the initial thickness d _n0 obtained by drying, after exposure with an exposure amount E _n, after further development When the remaining film thickness is d _n and the curing start exposure dose is _{En 0} , the following equation (2) is obtained.
γ _n = (d _n / d _n0 ) / (logE _n −logE _n0 ) (2)
(However, _{E n} is selected from the range of Residual Film Ratio _(d n _{/ d n0)} from 20 to 80 percent comprising such an exposure amount.) A step of exposing the first photosensitive composition layer after the step of forming the first photosensitive composition layer and before the step of forming the second photosensitive composition layer. The method for forming a partition for a flat display according to claim 1. 3. The flat panel partition according to claim 1, wherein each of the first photosensitive paste and the second photosensitive paste includes an organic component and inorganic fine particles as essential components and low-melting glass fine particles as inorganic fine particles. Forming method. The method for forming a partition for a flat display according to claim 1, wherein the first photosensitive paste contains an ultraviolet absorber. The method for forming a partition for a flat display according to claim 1, wherein the first photosensitive paste contains a photo-fading compound. 6. The method for forming a partition for a flat display according to claim 5, wherein the photochromic compound is a photoacid generator. A method for manufacturing a flat display, wherein the method for manufacturing a flat display partition according to any one of claims 1 to 6 is used.