JP4797683B2 - Negative photosensitive paste and its manufacturing method, pattern forming method, and flat panel display manufacturing method. - Google Patents

Description

  The present invention relates to a negative photosensitive paste suitable for forming an insulating pattern used for flat display such as a plasma display panel, a field emission display, and a fluorescent display tube, a manufacturing method thereof, and a pattern forming method using the same. It is.

  In recent years, development of flat displays such as plasma display panels, field emission displays, fluorescent display tubes, liquid crystal display devices, electroluminescence displays, and light emitting diodes has been rapidly advanced. Among these, the plasma display generates a plasma discharge between the anode electrode and the cathode electrode facing each other in the discharge space provided between the front glass substrate and the rear glass substrate, and the gas sealed in the discharge space. Display is performed by irradiating the phosphor provided in the discharge space with the ultraviolet rays generated from the discharge. A gas discharge type display such as a plasma display or a fluorescent display tube requires an insulating partition for partitioning a discharge space. In addition, field emission displays such as field emission displays require an insulating coating for isolating the gate electrode from the cathode. In forming insulating partition walls such as these plasma display panels and field emission displays, materials and processing methods that can pattern an inorganic material such as glass powder with high accuracy are required.

In particular, regarding a plasma display, forming a finer partition wall to ensure a wider discharge space is an essential technique for increasing the brightness of the plasma display. Conventionally, as a method for performing fine pattern processing of an inorganic material, a method of forming a pattern by a negative photosensitive paste method has been proposed. (For example, patent document 1). The cross-sectional shape of the barrier rib for plasma display is preferably rectangular in order to secure a wider discharge space and suppress charge leakage to adjacent cells, but it is a negative photosensitive material containing inorganic fine particles dispersedly. In the paste coating film, scattering of exposure light is unavoidable, and the narrowness of the exposure tolerance (exposure margin) that causes problems such as thickening of the bottom of the pattern shape and the formation of residual film between patterns is an issue. there were. In general, the substrate used for the plasma display has a diagonal of 800 mm or more, and since the in-plane variation of the exposure amount in the exposure process is large, the variation in the bottom width of the partition wall in the surface tends to be large, and flickers when the panel is lit. And brightness spots may occur. In order to eliminate such thickening of the bottom of the pattern, it has been proposed to add an ultraviolet absorber having light absorption in the ultraviolet region to the negative photosensitive paste (Patent Document 2). Even so, the exposure amount margin is insufficient, or the sensitivity of the negative photosensitive paste is lowered due to the absorption of exposure light by the ultraviolet absorber. Furthermore, when the exposure amount is less than the minimum exposure amount, the bottom of the pattern does not increase, but the line width becomes narrow, so that the pattern is easily peeled off during the development process, and the exposure amount margin is narrow.
JP-A-5-342992 (Claim 1) JP 11-249293 A (Claim 1)

  The present invention pays attention to the above-mentioned problems of the prior art, and forms a pattern such as a high-definition and high-aspect-ratio partition wall, so that there is no decrease in sensitivity of the negative photosensitive paste, and the exposure margin can be improved reliably. An object is to provide a negative photosensitive paste. Another object of the present invention is to provide a plasma display in which high-definition and high aspect ratio partition walls are formed.

  In order to solve the above problems, the present invention has the following configuration. That is, the present invention is achieved by a negative photosensitive paste comprising at least inorganic fine particles and an organic component, wherein the negative photosensitive paste contains a photo-fading compound as an organic component. In addition, this is achieved by a pattern forming method comprising applying the negative photosensitive paste so that the film thickness after drying becomes 150 μm or more, and then exposing, developing and baking at least.

  ADVANTAGE OF THE INVENTION According to this invention, the negative photosensitive paste which can reduce the sensitivity fall of a negative photosensitive paste is small, and can improve an exposure amount margin reliably can be provided. In addition, a plasma display in which high-definition and high-aspect-ratio barrier ribs are formed can be provided.

  The negative photosensitive paste as used in the present invention is a reaction such as photocrosslinking, photopolymerization, photodepolymerization, and photo-denaturation by irradiating the coating film after coating and drying with actinic rays. The photosensitive paste can be formed by changing the chemical structure and becoming insoluble in the developer, and then removing only non-irradiated portions with 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- Specific examples include laser beams having specific wavelengths such as a cadmium laser, a helium-neon laser, an argon ion laser, a semiconductor laser, a YAG laser, and a carbon dioxide gas laser.

  As a result of intensive studies on the formation of high-definition and high-aspect-ratio patterns, the inventors have found that this can be achieved with a negative photosensitive paste having the composition described below.

That is, the present invention is a negative photosensitive paste containing an organic component containing an alkali-soluble photosensitive polymer composed of inorganic fine particles and an acrylic copolymer , and has a glass transition temperature of 400 ° C. to 600 ° C. as inorganic fine particles. It is necessary to contain a low-melting glass powder and to contain a photochromic compound having a naphthoquinonediazide structure in the molecule as an organic component.

  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 the g-line (wavelength 436 nm), h-line (wavelength 405 nm), and i-line (wavelength 365 nm) of an ultra-high pressure mercury lamp. It is preferable that the photochromic compound also has absorption in the g-line, h-line and i-line regions. By adding a photo-bleaching compound to the negative photosensitive paste, it prevents the exposure light from entering the non-exposed area that is not exposed to exposure light in pattern design, and suppresses the bottom thickness of the pattern. Can do. Further, in the exposed portion, the photochromic compound absorbs the energy of the exposure light and does not gradually absorb through photodecomposition or photomodification, so that sufficient exposure light easily reaches the lower layer. Therefore, the photocuring contrast between the non-exposed portion and the exposed portion becomes clear, and the exposure amount margin can be reliably 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 fading dyes, photoacid generators, photobase generators, and nitrone compounds, and photomodifying compounds such as azo dyes and photochromic compounds.

  In the present invention, a photoacid generator can be particularly preferably used as the photo-fading compound. The photoacid generator is widely used in a positive photosensitive paste method in which a pattern is formed using a resin that dissolves in a developer due to the presence of an acid, but when used in a negative photosensitive paste, As described above, not only can the exposure amount margin be improved, but when applied to a negative photosensitive paste using an alkaline developer, acid is generated by exposure light, so that the acidic part of the alkali-soluble component of the negative photosensitive paste is generated. Is deionized, so that 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, and 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 sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds, and the like, and preferred 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 compound having a naphthoquinonediazide structure is particularly preferably used as a photoacid generator from the viewpoint of heat resistance during film formation drying and low residue properties during baking. 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 -Diazido-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 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, 1,2-naphthoquinone-2-diazide-4-sulfonic acid and 1,2-naphthoquinone-2-diazide-5 -Amides of sulfonic acids with esters of 2,3,4,4'-tetrahydroxybenzophenone or 1,1,1-tris (4-hydroxyphenyl) ethane, diaminodiphenyl ethers, 1,2-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) Examples include esters with ethane and amides with diaminodiphenyl ether. 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. Is mentioned.

  Similarly, a photochromic compound is a compound that reversibly colors or fades through photo-denaturation 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.

  Nitrone compounds are also compounds that fade with light and can be preferably used as photochromic compounds. Known nitrone compounds can be used, and examples thereof include phenyl nitrone derivatives and naphthyl nitrone derivatives.

  In forming an insulating pattern for a flat display, after forming a pattern by exposure and development, firing is performed to decompose the organic matter and sinter inorganic fine particles to complete the insulating 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 minutes / minute. 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.

  In addition, after the negative photosensitive paste is uniformly applied on the substrate, it is formed by drying at about 60 to 150 ° C. for 10 to 120 minutes, depending on the type and film thickness of the organic solvent in the paste. . 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.

Of the g-rays, h-rays, and i-rays that are commonly used exposure rays, the h-rays and i-rays are largely absorbed by photosensitive organic components such as photopolymerization initiators and are absorbed by the surface of the coating. It is difficult to reach the lower layer. Therefore, in order to clarify the contrast between the exposed part and the non-exposed part, it is effective to make the g-line transmittance in the exposed part higher than the g-line transmittance in the non-exposed part.
In the present invention, when the negative photosensitive paste is applied and dried to form a coating film having a thickness of 150 μm, the total light transmittance at a wavelength of 436 nm is defined as T ₁ (%), and the coating film is exposed to an exposure amount of 200 mJ / When the total light transmittance after exposure at cm ² is T ₂ (%), it is preferable that T ₁ and T ₂ satisfy the following formula (1).
5 <T ₂ −T ₁ <20 (1)
Further, it is more preferable to satisfy the following formula (2).
7 <T ₂ −T ₁ <15 (2)
When T ₂ -T ₁ is 5% or less, the contrast between the exposed portion and the non-exposed portion is not clear, and the effect of suppressing the bottom thickening cannot be expected so much. On the other hand, if it is 20% or more, the photo-fading compound is faded by weak scattered light in the vicinity of the boundary between the non-exposed portion and the exposed portion, and the bottom of the pattern is likely to be thickened. By setting T ₂ -T ₁ in the above range, it is possible to obtain a negative photosensitive paste having a large exposure dose margin and having no particularly thick bottom of the pattern.
It is preferable that the total light transmittance T ₂ of the exposed portion is 10% or more, more preferably 15% or more. If T ₂ is less than 10%, the bottom rear narrow lower paste coating becomes insufficient curing, requires attention because it may cause pattern at the development peeling.

One type of photochromic compound that can be used in the present invention may be used alone, or two or more types may be mixed and used. The compounding amount of the photochromic compound is preferably in the range of 0.001 to 1% by mass with respect to the negative photosensitive paste, although it depends on the absorbance of the photochromic compound before exposure. If it is 0.001% by mass or less, the T ₂ -T ₁ is less likely to exceed 5%, and the bottom of the pattern tends to be thickened. On the other hand, when the content is 1% by mass or more, the g-line hardly reaches the lower layer part, and the sensitivity of the negative photosensitive paste is lowered. In order for the photochromic compound to function properly as a contrast enhancer, it is more preferable to blend in the range of 0.002 to 0.5 mass%.

  The photochromic compound has the function of improving the light transmittance of the exposed part and enhancing the contrast between the exposed part and the non-exposed part, but absorbs the light scattered by the inorganic fine particles and changes the structure such as photodecomposition and photomodification. After that, the scattered light can no longer be absorbed. Therefore, it is preferable to further contain an ultraviolet absorber as an organic component of the negative photosensitive paste of the present invention. Here, the ultraviolet absorber refers to a substance that absorbs a wavelength of 300 to 500 nm and releases the absorbed light energy as an inactive radiation (thermal energy). After absorption, it absorbs light through photolysis or photodenaturation. It is to be distinguished from a photo-fading compound in which the color is lowered. Since the ultraviolet absorber absorbs excessive scattered light, it is possible to suppress an increase in the bottom of the pattern and further increase the exposure amount margin.

  Ultraviolet absorbers are particularly effective as long as they have excellent absorbance at wavelengths near the g-line, h-line and i-line. Specific examples include benzophenone compounds, cyanoacrylate compounds, salicylic acid compounds, and 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.

  As for content of a ultraviolet absorber, 0.001-1 mass% is preferable in a paste, More preferably, it is 0.001-0.5 mass%. By making the addition amount of the ultraviolet absorber within this range, it is possible to absorb the scattered light, suppress the pattern bottom thickness, and maintain the sensitivity to the exposure light.

  The negative photosensitive paste of the present invention preferably contains a silane coupling agent or a titanium coupling agent (hereinafter referred to as a coupling agent). 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 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. Normally, a pattern with a width of 60 μm is easily peeled off by development, but the addition of a silane coupling agent or a titanium coupling agent can improve the exposure margin even when forming a high-definition pattern with a width of 50 μm or less. it can. Hereinafter, the silane coupling agent will be specifically described.

  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, one kind of these coupling agents may be used alone, or two or more kinds may be used in combination. Moreover, you may use the self-condensate using 1 type of coupling agents, and the heterogeneous condensate which combined 2 or more types.

  In this invention, it is preferable that the weight average molecular weights of a coupling agent are 200-1000, and it is more preferable that it is 250-500. When the weight average molecular weight is 200 or more, evaporation during drying of the paste coating film can be suppressed, and when it is 1000 or less, the thermal decomposability during firing can be kept good.

  The coupling agent preferably has a weight retention of 80% by mass or more when it is heated from 30 ° C. to 100 ° C. at 10 ° C./min and then held at 100 ° C. for 2 hours. By setting it to 80% by mass or more, the volatilization of the coupling agent during drying of the paste coating film is suppressed, and the adhesion between the glass substrate and the pattern after drying is improved, so that an exposure margin can be obtained even when a high-definition pattern is formed. Can be improved. Even at room temperature, the coupling agent chemically binds to inorganic fine particles contained in the negative photosensitive paste through a condensation reaction, etc., and becomes non-volatile, so that the weight retention of the coupling agent alone is 80% by mass or more. It is sufficient if it is present, but it is possible to more preferably use 90% by mass or more.

  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. The coupling agent having these organic functional groups also acts as a radical polymerizable monomer and can improve the degree of photocuring in the vicinity of the boundary between the inorganic fine particles and the organic component at the time of exposure. The meandering of the pattern can be suppressed.

  In this invention, it is preferable to heat-process the negative photosensitive paste containing a coupling agent at 70-90 degreeC for 30 minutes-2 hours before application | coating. By performing the heat treatment at 70 ° C. or more for 30 minutes or more, the condensation reaction between the inorganic fine particles and the coupling agent can be dramatically accelerated, and the development resistance of the exposed portion can be improved. In addition, since the inorganic fine particles and the coupling agent react gradually at room temperature, the viscosity of the negative photosensitive paste gradually increases due to the gelation mechanism. By completing the reaction, an increase in viscosity can be prevented, and a negative photosensitive paste with 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 organic component used in the present invention is a portion obtained by removing the inorganic component from the paste, and is preferably contained in an amount of 5 to 50% by mass in the paste. By setting it within this range, pattern processing on a substrate by a photolithography method using a negative photosensitive paste containing inorganic fine particles becomes possible.

  The organic component is a photosensitive organic material selected from at least one of a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer in addition to the above-described photo-fading compound, ultraviolet absorber, silane coupling agent, or titanium coupling agent. Add ingredients such as ingredients, antioxidants, organic dyes, photopolymerization initiators, sensitizers, sensitization aids, plasticizers, thickeners, dispersants, organic solvents, suspending agents as needed It is composed of that.

  An alkali-soluble polymer can be preferably used as the photosensitive polymer. This is because the polymer is alkali-soluble, so that an aqueous alkaline solution can be used as a developer 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 into methacrylates Listed are alternatives 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 by adding these 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 double bond include a vinyl group, an allyl group, an acrylic group, and a methacryl group. In order to add such a functional group to the polymer, a compound having a glycidyl group or an isocyanate group and a carbon-carbon double 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 double 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 double bond include acryloyl isocyanate, methacryloyl isocyanate, acryloylethyl isocyanate, and methacryloylethyl isocyanate.

  The photosensitive monomer is a compound containing a carbon-carbon unsaturated bond. 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 , Isobornyl 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, Trifluoroethyl 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, di Pentaerythritol hexaac Rate, dipentaerythritol monohydroxypentaacrylate, ditrimethylolpropane tetraacrylate, glycerol diacrylate, methoxylated cyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, triglycerol diacrylate, trimethylolpropane Triacrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, benzyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, bisphenol A diacrylate, diacrylate of bisphenol A-ethylene oxide adduct, bisphenol A-propylene oxide Adjunct Diacrylate, 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-methyl Styrene, m-methyl styrene, chlorinated styrene, brominated styrene, α-methyl styrene, chlorinated α-methyl styrene, brominated α-methyl styrene, chloromethyl styrene, hydroxymethyl styrene, carboxymethyl styrene, vinyl naphthalene, Examples include vinyl anthracene, 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, 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.

  As the photopolymerization initiator, a photoradical initiator that generates radicals upon irradiation with an active light source 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, benzyldimethylketanol, 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 Quinolinesulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylformine, camphorquinone, carbon tetrabrominated, tribromophenyl sulfone, peroxidation Examples thereof include a combination of a photoreductive dye such as benzoin, eosin and methylene blue and a reducing agent such as ascorbic acid and triethanolamine. In the present invention, one or more of these can be used. A photoinitiator is 0.05-20 mass% with respect to the total amount of a photosensitive monomer and a photosensitive polymer, More preferably, it adds in 0.1-15 mass%. If the amount of the polymerization 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, a sensitizer can be used with a photoinitiator, a sensitivity can be improved or the wavelength range effective for reaction can be expanded. 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 an 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.

  In the present invention, an antioxidant is preferably added. 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. Since the reaction is suppressed and a photoreaction occurs abruptly at an exposure amount that cannot be suppressed by the antioxidant, it is possible to increase the contrast of dissolution and insolubility in the developer. Specifically, p-benzoquinone, naphthoquinone, p-xyloquinone, p-toluquinone, 2,6-dichloroquinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicaproxy-p-benzoquinone, hydroquinone, p-t -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, picric acid, quinonedioxime, Lohexanone oxime, pyrogallol, tannic acid, triethylamine hydrochloride, dimethylaniline hydrochloride, cuperone, 2,2′-thiobis (4-tert-octylphenolate) -2-ethylhexylaminonickel- (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-trihydroxybenzene, etc. Although it is mentioned, it is not limited to these. In the present invention, one or more of these can be used. The addition amount of the antioxidant is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass in the photosensitive paste. By making the addition amount of the antioxidant within this range, it is possible to maintain the photosensitivity of the photosensitive paste, and maintain the degree of polymerization and maintain the pattern shape, while increasing the contrast between the exposed portion and the non-exposed portion. it can.

  An organic solvent is used to adjust the viscosity at the time of applying the photosensitive paste to the substrate 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 inorganic fine particles in the present invention are fine particles of conductive powders such as glass and ceramics and Au, Ag, Pd, Pt, and the like, and particularly useful when glass powder is used.

  As glass powder, it is preferable to contain the low melting glass powder whose glass transition temperature is the range of 400-600 degreeC. This is because the glass transition point is in this range, the pattern is not deformed during sintering, and the meltability is appropriate. Moreover, the pattern processing on the board | substrate used for a normal display is possible by containing 50 mass% or more of glass powder in a paste. A more preferable range of the glass transition temperature is 430 to 550 ° C.

  By using a low melting point glass powder having such a glass transition temperature and blending a metal oxide so that the refractive index of the glass powder is 1.50 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 powder is selected in consideration of the shape of the pattern to be produced. The 50% particle size (average particle size) in the weight distribution curve is 1.0 to 3.0 μm, the top size. It is preferable that it is 15 micrometers or less. Further, it is preferable that the 10% particle diameter is 0.5 to 1.5 μm and the 90% particle diameter is 4.0 to 8.0 μm. More preferably, the average particle size is 1.5 to 2.5 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. An average particle size of less than 1.0 μm is not preferable because light scattering tends to be intense during exposure.

The low-melting glass powder that can be preferably used as the inorganic fine particles has, 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 because it can lower the refractive index of the glass and prevent 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. Moreover, when using a glass substrate as a base material, 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, when a thermal expansion coefficient is suppressed small and it bakes on a glass substrate, a crack does not arise. 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 maintained 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. The devitrification by crystallization can also be prevented by setting it as 2 mass% or more. 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 also 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, glass transition temperature 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 powder, 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 to a fine powder 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 glass powder, high-resistance and dense pores can be obtained by using powders that are made of ultra-pure alkoxide and organometallic materials with a purity of 99.99% or more, and that are homogeneously produced by the sol-gel method. This is preferable because a high-purity insulating layer with less content can be obtained.

  Moreover, it is preferable to contain a filler component in addition to the low softening point glass powder as the inorganic fine particles of the negative 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. The filler component has an average particle diameter of 1 to 4 μm and an average refractive index of 1.4 to 1.7 in consideration of dispersibility and filling properties in the negative photosensitive paste and suppression of light scattering during exposure. It can be preferably used. In the present invention, as such a filler component, at least one selected from a high melting point glass powder having a glass transition temperature of 500 ° C. or higher and a ceramic powder such as cordierite, alumina, silica, magnesia, and zirconia is used. However, from the viewpoint of easy adjustment of the average particle diameter and average refractive index, it is preferable to use a high melting point glass powder.

  When using a high melting point glass powder, it is preferable to add a glass transition temperature of 500 to 1200 ° C. in a composition range of 3 to 40% by mass with respect to all inorganic fine particles. When the amount is less than 3% by mass, the edge of the pattern tends to collapse during firing, and a pattern with a good shape may not be obtained. On the other hand, when the amount is more than 40% by mass, the denseness of the pattern to be formed tends to decrease, which is not preferable.

  Moreover, the negative photosensitive paste of this invention can be preferably used also for conductive pattern formation by providing electroconductivity. When used for forming a conductive pattern, it is a preferred practical form to use fine particles of conductive powder such as Au, Ag, Pd, and Pt as inorganic fine particles. Au, Ag, Pd, and Pt can be used alone or as a mixed powder. For example, Ag (30-80) -Pd (70-20), Ag (40-70) -Pd (60-10) -Pt (5-20), Ag (30-80) -Pd (60-10) -Cr (5-15), Pt (20-40) -Au (60-40) -Pd (20), Au (75-80) -Pt (25-20), Au (60-80) -Pd ( 40-20), Ag (40-95) -Pt (60-5), Pt (60-90) -Rh (40-10) (above, () represents mass%), etc. A ternary mixed precious metal powder is used. Among these, those to which Cr or Rh is added are preferable in that high temperature characteristics can be improved.

  The average particle size of these conductive inorganic fine particles is preferably 0.5 to 5 μm. By setting the average particle size to 0.5 μm or more, light rays can be smoothly transmitted through the coated film during ultraviolet exposure, and a fine pattern with a good conductor line width of 60 μm or less can be formed. On the other hand, when the thickness is 5 μm or less, the unevenness of the surface of the circuit pattern after coating is not roughened, the pattern accuracy is improved, and noise generation can be suppressed.

In order to obtain a fine circuit pattern of 10 to 40 μm after development by coating the conductive pattern and sufficiently transmitting ultraviolet light without being scattered before exposure and effectively working, the conductive powder has an average particle diameter of 1 to 1 It is preferable that it is 4 micrometers and a specific surface area is 0.1-5 m < ² > / g. More preferably, the average particle diameter is 0.8 to 4 μm and the specific surface area is 0.5 to 1.5 m ² / g. When it is within this range, there is no generation of a residual film of the conductor film in the non-exposed portion during development, and a particularly highly accurate circuit pattern can be obtained.

The specific surface area of the noble metal conductive fine particles is preferably 0.1 to ³ m ² / g. By setting the specific surface area to 0.1 m ² / g or more, the accuracy of the circuit pattern can be improved. Moreover, by setting it as 3 m < ² > / g or less, scattering of an ultraviolet-ray can be prevented and a pattern precision can be improved.

  As the shape of the noble metal conductive fine particles, flakes (plates, disks, rods) or spherical shapes can be used, but spherical shapes are preferable because aggregation is suppressed. In the case of a spherical shape, the scattering of ultraviolet rays at the time of exposure is small, so a highly accurate pattern can be obtained and the irradiation energy can be reduced.

  It is also a preferred embodiment of the present invention to use inorganic fine particles that have been surface-treated with the above-described 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, and a direct coupling agent The spray method etc. which spray can be mentioned.

  The negative photosensitive paste of the present invention contains predetermined components such as a photochromic 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 preparing the composition so as to have the following composition. The preliminary mixing can be preferably applied by hand stirring, a magnetic stirrer, or a mechanical stirrer. In addition, when adding a photosensitive polymer, it may be added directly to the dispersion, but it is possible to add a photosensitive polymer solution in which a photosensitive polymer is dissolved in an organic solvent in advance to obtain a uniform negative photosensitive paste. Is preferable. Next, main kneading is performed using a kneading machine such as a three-roller, and the mixture is homogeneously dispersed to produce a negative photosensitive paste. Moreover, it is also preferable to filter the negative photosensitive paste after the main kneading using a filter having an opening of 1 to 20 μm. Furthermore, it is also preferable to defoam the negative photosensitive paste using a kneading / degassing machine or a vacuum stirrer.

  The negative photosensitive paste of the present invention thus obtained can be used for pattern formation of flat display members. In particular, when used as a member for a plasma display, a negative photosensitive paste is applied on a substrate, a pattern is formed through exposure and development, and further baked to obtain a member for a plasma display. The plasma display member and the manufacturing procedure of the plasma display are described below. Here, the basic structure and the like will be described using the most common alternating current (AC) plasma display as an example of the plasma display, but the plasma display is not necessarily limited thereto. In addition, the case where the barrier rib is formed using the negative photosensitive paste of the present invention will be described below, but the present invention is not limited to this and is also applicable to the formation of a pattern using a photolithography method such as an electrode pattern. can do.

  The plasma display is a member formed by sealing the front plate and the rear plate so that the phosphor layer formed on the front plate and / or the rear plate faces the inner space. The discharge gas is sealed in the tube. That is, on the front plate, a transparent electrode (sustain electrode, scan electrode) for display discharge is formed on the substrate on the display surface side. Because of the discharge, the gap between the sustain electrode and the scan electrode should be relatively narrow. A bus electrode may be formed on the back side of the transparent electrode for the purpose of forming a lower resistance electrode. However, the bus electrode is made of Ag, Cr / Cu / Cr or the like and is often opaque. Therefore, unlike the transparent electrode, it interferes with the display of the cell, and is preferably provided at the outer edge of the display surface. In the case of an AC type plasma display, a transparent dielectric layer and an MgO thin film as a protective film are often formed on the upper layer of the electrode. On the back plate, electrodes (address electrodes) for selecting cells to be displayed are formed. The partition walls and phosphor layers for partitioning the cells may be formed on either or both of the front plate and the back plate, but are often formed only on the back plate. In the plasma display, the front plate and the back plate are sealed, and an internal space between the two is filled with a discharge gas such as Xe-Ne or Xe-Ne-He.

  First, regarding the member manufacturing process, a method for manufacturing the front plate 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 powder, 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 powder include metal powder and metal oxide powder. As the metal powder, 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 electrode forming substrate by screen printing, bar coater, roll coater, die coater, blade coater, spin coater, or the like. After application, the thick film can be formed by drying using an optional oven such as a ventilating oven, a hot plate, an infrared drying oven, or vacuum drying. 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 the back substrate will be described. As the glass substrate, “PD200” manufactured by Asahi Glass or “PP8” manufactured by Nippon Electric Glass, which is a heat-resistant glass for plasma display, can be used in addition to soda glass. An address stripe electrode pattern is formed on a glass substrate 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 powder and 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 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. Furthermore, it is preferable to provide a dielectric layer on the address electrode. 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. In addition, as a method of forming the dielectric layer, a dielectric paste mainly composed of inorganic fine particles such as glass powder and high melting point glass powder and an organic binder is printed or applied by screen printing, a slit die coater or the like. There is.

  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 or the like is preferable. First, a partition paste made of the negative photosensitive paste of the present invention is applied on a substrate on which a dielectric is formed. As a coating method, methods such as a bar coater, a roll coater, a slit die coater, a blade coater, and screen printing 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. In this invention, it is preferable to apply | coat so that the application | coating thickness after drying may be 150 micrometers or more. By setting the thickness to 150 μm or more, a sufficient discharge space is obtained, and the brightness of the plasma display can be improved by expanding the application range of the phosphor.

  The applied partition paste is dried and then exposed. In general, the exposure is performed through a photomask, as in normal photolithography. 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, after applying a negative photosensitive paste on a substrate such as a glass substrate, exposure is performed while being conveyed, thereby exposing a large area with an exposure machine having a small exposure area. be able to. 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 .

  Further, in the pattern forming method of the present invention, a dielectric paste containing a low-melting glass powder having a glass transition temperature in the range of 400 ° C. to 600 ° C. and an ultraviolet absorber is applied onto a substrate and dried, After the negative photosensitive paste is applied on the dielectric paste coating film, at least exposure, development, and baking may be performed.

  A dielectric paste coating film is formed as an underlayer for the negative photosensitive paste coating film during exposure, and the coating film contains an ultraviolet absorber, which suppresses the thickening of the bottom of the pattern. It becomes easy. As an ultraviolet absorber that can be used for the dielectric coating film, an ultraviolet absorber that can be used for the above-described negative photosensitive paste can be used, and the absorption intensity at a wavelength of 365 nm is a region of a wavelength of 436 nm to 405 nm. By using an ultraviolet absorber having a smaller absorption intensity than that, the exposure margin is particularly good and the bottom thickness can be suppressed. Examples of the ultraviolet absorber having such characteristics include organic dyes having absorption characteristics corresponding to red, orange, and yellow. Specifically, C.I. I. Common names include SR (solvent red) -179, SO (solvent orange) -60, 80, SY (solvent yellow) -14, and the like.

  Furthermore, the thermal characteristics of the ultraviolet absorber preferably have the following characteristics from the viewpoint of compatibility with the pattern forming process. That is, the dielectric coating film needs to be dried and thermally cured at a temperature of 120 to 200 ° C. so that peeling or cracking does not occur in the negative photosensitive paste development described below. Therefore, as a particularly usable ultraviolet absorber, those having thermal characteristics that do not volatilize at the heat treatment temperature of drying and thermosetting are desirable. Further, since the light emission characteristics of the PDP may change due to the ultraviolet absorber or the residue remaining in the dielectric layer after the dielectric layer has undergone the firing step, those that volatilize in the firing step are preferable.

  The proportion of the UV absorber contained in the dielectric paste should not hinder the drying and thermal curing of the coating film when the dielectric is heat-treated, and the center exposure amount during pattern formation should not be excessively increased. However, it is generally about 0.05 to 1% by mass with respect to the solid content of the dielectric paste obtained by removing the solvent from the dielectric paste.

  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 capable of dissolving the organic components in the negative photosensitive paste can be used. However, when a compound having an acidic group such as a carboxyl group is present in the negative photosensitive paste, an alkaline aqueous solution is used. Can be developed. 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.

  Moreover, it is also preferable that the partition wall is composed of two or more layers. By using a structure of two or more layers, the configuration range of the partition wall shape can be expanded three-dimensionally. For example, in the case of a two-layer structure, the first layer is applied and exposed in a stripe shape, then the second layer is applied, the first layer is exposed to a stripe shape in the vertical direction, and development is performed, thereby causing unevenness. It is possible to form a partition wall having a cross-beam structure. In this case, the content of the photo-fading compound in the negative photosensitive paste forming each layer may be changed.

Next, after baking by holding at a temperature of 520 to 620 ° C. for 10 to 60 minutes in a baking furnace, a phosphor is formed using the 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 powder is not particularly limited, but the following phosphors are preferable from the viewpoint 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 manufacturing a plasma display panel will be described. After sealing the back substrate and the front substrate of the present invention, after evacuating while heating the space formed between the two substrates, a discharge gas composed of He, Ne, Xe, etc. is sealed. 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.

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

A. Measurement of absorption maximum wavelength of photochromic compound and ultraviolet absorber Use a spectrophotometer (manufactured by Hitachi, Ltd., U-3410 self-recording spectrophotometer) for the UV-visible absorption spectrum of the photochromic compound or ultraviolet absorber. And measured. At this time, a sample prepared by dissolving 1 mg of a photo-fading compound or an ultraviolet absorber in 20 ml of γ-BL, and γ-BL in which nothing is dissolved is referred to, and 350 to 350 g which are near the g-line, h-line, and i-line The section of 500 nm was measured, and the peak top wavelength in the meantime was read.

B. 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.

C. Measurement of Glass Transition Temperature of Glass Fine Particles The glass transition temperature of the glass particles used was measured using a thermomechanical analyzer (manufactured by Seiko Instruments Inc., EXTER6000 TMA / SS). Glass particles were melted at 800 ° C. and processed into a cylindrical shape having a diameter of 5 mm and a height of 2 cm to obtain a measurement sample.

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

  Monomers, polymers, photopolymerization initiators, sensitizers, antioxidants, photo-fading compounds, UV absorbers and silane coupling agents are weighed in a specified amount, and then γ-BL is added as a solvent to adjust the viscosity. , Low melting point glass powder / filler = 80/20 (mass ratio), organic component excluding solvent / inorganic fine particles = 30/70 (mass ratio) and then kneading with a three roller kneader, It was a negative photosensitive paste. Table 1 shows the amount of the organic component added excluding the solvent. In Example 11, the low-melting glass powder 2 was used as the low-melting glass powder, and the low-melting glass powder 1 was used otherwise.

The raw material used for the negative photosensitive paste for barrier ribs is as follows.
Monomer 1: Trimethylolpropane triacrylate monomer 2: Tetrapropylene glycol dimethacrylate polymer 1: 0.4 equivalent of glycidyl with respect to the carboxyl group of the copolymer of methacrylic acid / methyl methacrylate / styrene = 40/40/30 Addition reaction of methacrylate (weight average molecular weight 43000, acid value 100)
Photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (IC369 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%)
Photochromic compound 2: A fulgide compound having the following structural formula was used. (Absorption maximum wavelength 390 nm, weight retention at 500 ° C .; 1.0 mass%, weight retention when held at 100 ° C. for 2 hours; 99.4%)

Photochromic compound 3: α- (4-diethylaminophenyl) -N-phenylnitrone (absorption maximum wavelength 388 nm, weight retention at 500 ° C .; 0.1 mass%, weight retention when held at 100 ° C. for 2 hours) Rate: 95.3%)
Photochromic compound 4: 4-hydroxyazobenzene-2′-carboxylic acid (manufactured by Tokyo Ohka Kogyo Co., Ltd., absorption maximum wavelength; 375 nm, weight retention at 500 ° C .; 0.1 mass%, held at 100 ° C. for 2 hours) Weight retention when 99.9%)
UV absorber 1: Sudan IV (Tokyo Ohka Kogyo Co., Ltd., absorption wavelength: 350 nm and 520 nm)
Ultraviolet absorber 2: BONASORB UA-3901 (manufactured by Orient Chemical Co., Ltd., absorption maximum wavelength; 395 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%)
Silane coupling agent 2: A product obtained by stirring and self-condensing silane coupling agent 1 at 60 ° C. for 30 minutes (weight average molecular weight: 3000, weight retention when held at 100 ° C. for 2 hours; 100%)
Inorganic fine particles:
Low melting glass powder 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 5% by mass (Glass transition temperature 491 ° C)
Low melting glass powder 2: Low melting glass powder surface-treated with silane coupling agent 1. The glass composition is the same as the low melting glass powder 1. The surface treatment was performed by immersing the low-melting glass powder in a 10% aqueous solution of the silane coupling agent 1 for 3 hours, filtering to remove the aqueous solution, and drying at 100 ° C.
Filler powder 1: A high melting point glass powder 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)
E. Measurement of total light transmittance (T ₁ , T ₂ ) of negative photosensitive paste coating film A negative photosensitive paste was applied on a glass substrate so that the thickness after drying was 150 μm, dried, and a spectrophotometer ( The total light transmittance was measured using a Hitachi Ltd. U-3410 self-recording spectrophotometer. Intermediate drying was performed at 100 ° C. for 10 minutes. Measurements 100% through the glass substrate using, reads the total light transmittance at a g-line 436 nm, and this value and T _1. Next, the substrate was exposed to 200 mJ / cm ² with an ultrahigh pressure mercury lamp with an output of 50 mW / cm ² without using an exposure mask, and then the total light transmittance at 436 nm was read in the same manner. the value was defined as _{T 2.}

F. Evaluation Evaluation of the central exposure E _c and exposure margin was performed by the following procedure. First, a negative photosensitive paste was applied on a glass substrate by multiple application / drying by a screen printing method so as to have a thickness of 150 μm after drying. Intermediate drying 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 be capable of forming a stripe-shaped barrier rib pattern in a plasma display with a pitch of 300 μm and a line width of 40 μm. Exposure, a super high pressure mercury lamp with an output of 50 mW / cm ² from 100 mJ / cm ² to 500 mJ / cm ^2, were UV exposure to 50 mJ / cm ² intervals. 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 is divided into five small substrates, one point is randomly selected on each small substrate, and a cross section perpendicular to the longitudinal direction of the partition is observed with a scanning electron microscope (S2400, manufactured by Hitachi, Ltd.). _b was measured 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 (%). As E _c is smaller it can be said to be highly sensitive. Further, in order to produce a high-definition plasma display with no lighting and flickering with a 42-inch or larger plasma display, the exposure dose margin is preferably 20% or more.

F. 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. Address electrode patterns were formed on a “PD-200” glass substrate (42 inches) manufactured by Asahi Glass Co., Ltd. by a photolithography method using a photosensitive silver paste. Next, a dielectric layer having a thickness of 20 μm was formed on the glass substrate on which the address electrodes were formed by screen printing. Thereafter, the negative photosensitive paste was uniformly applied on the back plate glass substrate on which the address electrode pattern and the dielectric layer were formed by screen printing until a desired thickness was obtained. In order to avoid the occurrence of pinholes and the like in the coating film, coating and drying were repeated several times or more so that the thickness after drying was 150 μm. Intermediate drying was performed at 100 ° C. for 10 minutes. Subsequently, using the above-described negative chrome mask, UV exposure was performed with an ultrahigh pressure mercury lamp having an output of 50 mW / cm ² from the upper surface. The exposure amount was E _c (mJ / cm ² ) determined above.

  Next, a 0.3% by weight aqueous solution of ethanolamine maintained at 35 ° C. was developed by applying it for 150 seconds in a shower, and washed with water using a shower spray to remove the uncured space. 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.

G. 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 within one, the display characteristics are A if it is within 2-4, and the display characteristics are not suitable if it is within 5-7. Appropriate, B, 8 or more is not possible as a display panel, and C.

(Example 1 , Reference Examples 1-3 )
Table 1 shows the results when a negative photosensitive paste containing a photobleaching compound was used. In Example 1, the photochromic compound 1 had a naphthoquinone diazide moiety in the molecule, was excellent in photochromic property in the g-line region, and had a large exposure dose margin. The photobleaching compound 2 is a compound having a reversible photobleaching property in the g-line region. In Reference Example 1 using this compound, an exposure amount margin similar to that in Example 1 was obtained. Furthermore, since the photochromic compound 3 has a low heat-resistant temperature, the exposure margin in Reference Example 2 using it was slightly better than that in Example 1, but it was good. Since the photo-fading compound 24 does not have a naphthoquinone diazide site in the molecule and a slight fading is observed in the i-line region, in Reference Example 3 using this, T ₂ -T ₁ is 4%, Although the exposure amount margin was lower than that in Example 1, it was not problematic.

(Examples 2 to 3 )
Table 1 shows the results when using a negative photosensitive paste containing a photobleaching compound and an ultraviolet absorber. Although the sensitivity was slightly reduced by using the photochromic compound and the ultraviolet absorber in combination, the exposure amount margin could be greatly increased, and no erroneous lighting of the panel was observed.

(Examples 4 to 5 )
Table 2 shows the results when a negative photosensitive paste containing a photo-fading compound and a silane coupling agent was used. Since the silane coupling agent is included, the minimum exposure amount can be lowered, and the exposure amount margin is larger than that in Example 1. Moreover, self-condensed, Example 5 using the weight average molecular weight is greater silane coupling agent 2, since the adhesive function of the silane coupling agent is not sufficiently obtained, expanding the width of the exposure margin than that of Example 4 There were few.

(Example 6 )
Table 2 shows the results when using a negative photosensitive paste containing any of the photobleaching compound, the ultraviolet absorber and the silane coupling agent. Since the silane coupling agent was included, the exposure amount margin was further expanded as compared with Example 2 . In addition, there was no significant reduction in sensitivity or erroneous lighting of the display.

(Example 7 )
The same evaluation as in Example 4 was performed except that the mixture was heated and stirred at 80 ° C. for 1 hour before kneading with a three-roller kneader during paste preparation. The results are shown in Table 2. Since the heat treatment was performed, the exposure margin was more effectively expanded and the display characteristics were excellent.

(Example 8 )
The same evaluation as in Example 4 was performed except that the low-melting glass powder 2 subjected to surface treatment with a silane coupling agent was used as the low-melting glass powder. The results are shown in Table 2. By using a glass powder subjected to surface treatment, T ₂ has been slightly reduced compared with Example 1, enlarged exposure margin was also excellent display characteristics.

(Examples 9 to 11 )
Evaluation was performed in the same manner as in Example 1 except that the addition amount of the photochromic compound was changed. The results are shown in Table 2. In Example 9, the amount added was small, and T ₂ -T ₁ was 6%. In Example 11, the amount added was large, and T ₂ -T ₁ was 16%. There wasn't. In Example 10 , T ₂ -T ₁ was 13%, and the exposure amount margin was also good.

(Examples 12 to 14 )
Pattern Forming Method F. In this method, instead of directly applying a negative photosensitive paste on a glass substrate, a dielectric paste having the composition shown in Table 3 is applied on the glass substrate and then heat-treated at 160 ° C. for 30 minutes. Evaluation was performed in the same manner as in Example 1 except that a negative photosensitive paste film was formed on the dielectric paste coating film. The results are shown in Table 4. Example 12 in which the ultraviolet absorber was not included in the dielectric paste coating film had almost the same exposure amount margin and display characteristics as Example 1. In the case of Example 13 , in which the dielectric coating film contains the ultraviolet absorber 1 in which the absorption intensity of i-line and the absorption intensity of h-line and g-line are substantially the same, the exposure amount margin is improved as compared with Example 1. However, the center exposure amount Ec shifted to the high exposure amount side within the allowable range. The display characteristics were good. In the case of Example 14 where the dielectric coating film contains the ultraviolet absorber 3 which is an ultraviolet absorber whose absorption intensity in the i-line region is smaller than the absorption intensity at a wavelength of 405 to 436 nm, the exposure amount margin is larger than that in Example 1. Improved, Ec and display characteristics were comparable.
The raw materials used for the dielectric paste are as follows. After weighing a predetermined amount of polymer, monomer, thermal polymerization initiator, dispersant, ultraviolet absorber, low melting point glass powder, filler powder, γ-BL is appropriately added as a solvent to adjust the viscosity. And kneaded to obtain a dielectric paste. Table 3 shows the amount of the organic component added excluding the solvent.
Thermal polymerization initiator: 1-1′-azobis (cyclohexane-1-carbonitrile)
Polymer 2: ethyl cellulose, number average molecular weight 80,000
Monomer 2: Tetrapropylene glycol dimethacrylate Dispersant: Adecatol SO-135 (Asahi Denka Co., Ltd.)
UV absorber 1: Sudan IV (Tokyo Ohka Kogyo Co., Ltd., absorption wavelength: 350 nm and 520 nm)
Ultraviolet absorber 3: PLASTOrange-8150 (Arimoto Chemical Industry Co., Ltd., CI general name; SO-60)
Inorganic fine particles:
Low melting glass powder 3: 40.15% by mass of zinc oxide, 33.3% by mass of boron oxide, 12.00% by mass of potassium oxide, 11.30% by mass of silicon oxide, 2.2% by mass of sodium oxide, 0. Glass powder consisting of 50% by mass. Glass transition temperature 459 ° C., 50 mass% particle size 2.9 μm.
Filler powder 2: Titanium oxide. 50% by mass particle size 2.5 μm.

(Comparative Example 1)
Table 4 shows the results when using a negative photosensitive paste that does not contain any of the photo-fading compound, the ultraviolet absorber, and the silane coupling agent. The total light transmittance of the coating film was high and the sensitivity was also higher than that of Example 1, but the exposure amount margin was remarkably lowered and display characteristics were not possible.

(Comparative Examples 2 to 4)
Table 3 shows the results in the case of using a photosensitive paste containing no UV-absorbing compound and containing an ultraviolet absorber and / or a silane coupling agent. When the ultraviolet absorber was included, the exposure amount margin was improved as compared with Comparative Example 1, but it was still insufficient and many erroneous lightings were observed. When the silane coupling agent was included, the minimum exposure amount was low and the exposure amount margin was slightly improved, but display characteristics were not possible.

(Comparative Example 5)
Pattern Forming Method F. In FIG. 1, instead of directly applying the negative photosensitive paste on the glass substrate, a dielectric having the same composition as in Example 13 is applied on the glass substrate, followed by heat treatment at 160 ° C. for 30 minutes. Evaluation was conducted in the same manner as in Comparative Example 4 except that a negative photosensitive paste film was formed on the dielectric coating film. Although the exposure amount margin is slightly improved as compared with Comparative Example 3, the display characteristics are not possible.

Claims (13)

A negative photosensitive paste containing an organic component containing an alkali-soluble photosensitive polymer composed of at least inorganic fine particles and an acrylic copolymer, and having a glass transition temperature of 400 ° C. to 600 ° C. as the inorganic fine particles. A negative photosensitive paste characterized by containing a glass powder and a photochromic compound having a naphthoquinonediazide structure in the molecule as an organic component. When the negative photosensitive paste is applied and dried to form a coating film having a film thickness of 150 μm, the total light transmittance at a wavelength of 436 nm is T ₁ (%), and the coating film is exposed to an exposure amount of 200 mJ using an ultrahigh pressure mercury lamp. / cm ² total light transmittance at a wavelength 436nm after exposure in the case that the _T 2 (%), the negative of claim _{1, T 1} and _{T 2} is characterized by satisfying the following formula (1) Type photosensitive paste.
5 <T ₂ −T ₁ <20 (1 ) Furthermore, the negative photosensitive paste of Claim 1 or 2 containing a ultraviolet absorber as an organic component . The negative photosensitive paste according to any one of claims 1 to 3, comprising a silane coupling agent or a titanium coupling agent. The negative photosensitive paste according to claim 4 , wherein the weight average molecular weight of the silane coupling agent or the titanium coupling agent is 200 to 1,000. Negative photosensitive paste according to claim 4 or 5 a silane coupling agent or titanium coupling agent is characterized by having at least one ethylenically unsaturated group in the molecule. A method for producing a negative photosensitive paste, comprising a step of heat-treating at 70 to 90 ° C for 30 minutes to 2 hours after mixing the negative photosensitive paste according to any one of claims 4 to 6. . The method for producing a negative photosensitive paste according to any one of claims 4 to 6 , wherein the inorganic fine particles are surface-treated with the silane coupling agent or the titanium coupling agent. . A pattern forming method comprising: applying the negative photosensitive paste according to any one of claims 1 to 6 so that a film thickness after drying becomes 150 μm or more, and then performing at least exposure, development, and baking. . Coating a dielectric paste having a glass transition temperature on the substrate contains a low melting point glass powder and an ultraviolet absorber is in the range of 400 ° C. to 600 ° C., dried, claim 1 in dielectric paste coating film 6 A pattern forming method comprising: applying the negative photosensitive paste according to any one of the above to a thickness of 150 μm or more after drying, followed by at least exposure, development, and baking. The pattern forming method according to claim 10, wherein the ultraviolet absorber has an absorption intensity at a wavelength of 365 nm smaller than an absorption intensity in a region of a wavelength of 436 nm to 405 nm. Method of forming a barrier rib pattern for a display using a method of forming a pattern according to claim 9-11. Method of manufacturing a patterned flat display panel using a forming method according to claim 9-11.