JP2006128092A - Patterning method, and method for manufacturing plasma display component and plasma display using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a patterning method in which the shape of a pattern is controlled to be a rectangle or trapezoid after firing a glass paste containing a large amount of low softening point glass and/or a glass paste free of filler. <P>SOLUTION: The patterning method comprises applying a paste containing an inorganic fine particle and an organic component, followed by patterning and firing. The paste containing 80 to 100wt% of a glass fine particle as an inorganic fine particle having a glass softening point between 350°C and 550°C, and 0 to 20wt% of a filler is applied and patterned into a reverse tapered shape, followed by firing to form a pattern of the shape of rectangular or trapezoid. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a pattern forming method. In particular, the present invention relates to a plasma display member and a method for forming an insulating layer, partition walls or electrodes for plasma display.

  In recent years, development of large flat panel displays such as DC-type and AC-type plasma displays, liquid crystal displays, and field emission displays has progressed, and some displays are already on the market and are forming a large market. A large flat panel display is formed with a structure having various functions such as pixel partitioning. For example, an AC type plasma display generates a plasma discharge between an anode and a cathode electrode facing each other in a discharge space provided between a front substrate and a rear substrate, and a Xe-Ne mixed gas sealed in the discharge space. The display is performed by irradiating a phosphor provided in the discharge space with ultraviolet rays having a very short wavelength such as 147 nm and 172 nm generated from a discharge gas such as the above.

  A PDP is superior to a CRT as a large screen panel of 40 inches or more in terms of depth and weight, but in order to achieve a higher display quality, it is desired to increase the brightness of the panel. High luminance can be achieved by increasing the partial pressure of Xe as a gas sealed in the discharge space, but simply increasing the partial pressure of Xe increases the discharge sustaining voltage of the PDP and increases the power consumption. There was a drawback. Therefore, in order to make up for such defects, the transparent dielectric formed on the front plate is patterned, and a transparent dielectric pattern is formed by thinning only the portion where discharge is performed, thereby preventing an increase in power consumption, high brightness, An efficient PDP is obtained.

The transparent dielectric pattern is formed by forming a pattern by a screen printing method, a sand blast method, a photolithography method, or the like, and firing the pattern. Conventionally, the pattern shape after baking of a partition and an electrode is controlled by containing a filler in glass paste (refer patent documents 1-3). However, since a transparent dielectric forms a transparent film after firing, if the glass paste contains a filler, bubbles are formed after firing, and the transparent dielectric does not become transparent due to light scattering by the bubbles. Therefore, there is a drawback that the filler cannot be contained, the pattern is distorted due to the fluidity of the low softening point glass during firing, and the pattern shape after firing cannot be maintained.
Japanese Patent No. 3440768 (Claim 1) Japanese Patent No. 3402070 (Claim 1) JP 2002-214772 A (Claim 1)

  Accordingly, the present invention aims to realize and provide a high-performance display member and display by paying attention to the above-mentioned problems of the prior art. Specifically, it is an object of the present invention to provide a pattern forming method in which the pattern shape after firing of a paste containing a large amount of low softening point glass becomes a rectangle or a trapezoid.

  In order to solve the above problems, the present invention has the following configuration. That is, the present invention is a pattern forming method in which a paste containing inorganic fine particles and an organic component is applied, baked after pattern formation, and 80 to 100% by weight of glass fine particles having a glass softening point of 350 ° C. to 550 ° C. as inorganic fine particles, In addition, a pattern forming method is characterized in that a paste containing 0 to 20% by weight of a filler is applied, followed by pattern formation in a reverse taper shape, and further baking to form a rectangular or trapezoidal pattern.

  The pattern shape after firing of the glass paste containing a large amount of low softening point glass and / or the glass paste containing no filler can be controlled to be rectangular or trapezoidal.

  The inventors have intensively studied a pattern forming method in which the pattern shape after firing of the paste containing a large amount of low-softening point glass is rectangular or trapezoidal, and as a result, found that this can be achieved by the forming method described below.

  That is, the present invention is a pattern forming method in which a paste containing inorganic fine particles and an organic component is applied, baked after pattern formation, and glass fine particles having a glass softening point of 350 ° C. to 550 ° C. are 80 to 100% by weight as inorganic fine particles. In addition, it is important to apply a paste containing 0 to 20% by weight of a filler, form a pattern in a reverse taper shape, and then perform baking to form a rectangular or trapezoidal pattern. The inorganic component of the paste in the present invention is inorganic fine particles of conductive powder such as glass, ceramics, Au, Ni, Ag, Pd, and Pt. Particularly useful in the present invention is when glass fine particles are used. is there. Here, the low softening point glass means a glass having a softening point of 600 ° C. or lower. In addition, the rectangle and trapezoid have corners or rounded edges, a shape with a taper angle of 45 to 80 degrees is a trapezoid, and a shape with an angle of 80 to 90 degrees is a rectangle. Here, the taper angle is θ shown in FIG.

Conventionally, many pastes contain 20% by weight or more filler in an inorganic component in order to maintain the pattern shape. The filler referred to here is glass fine particles having a softening point of 600 ° C. or more, ceramics, cordierite (2MgO · 2Al ₂ O ₃ · 5SiO ₂ ), Celsian (BaO · Al ₂ O ₃ · SiO ₂ ), anorthite ( CaO · Al ₂ O ₃ · 2SiO ₂ ), steatite (MgO—SiO ₂ ), spodumene (LiO ₂ · Al ₂ O ₃ · 4SiO ₂ ) and forsterite (2MgO · SiO ₂ ), silicon oxide, aluminum oxide, oxide Meaning inorganic fine particles such as titanium, zirconium oxide, yttrium oxide, cerium oxide, magnesium oxide, zinc oxide, manganese oxide, copper oxide, iron oxide, holmium oxide, lead oxide, tin oxide. If the filler is 20% by weight or less, the flowability of the low softening point glass is high, so that the pattern is distorted during firing. That is, when a pattern is formed with a paste containing 80% by weight or more of a low softening point glass in an inorganic component, it is difficult to maintain the shape before firing after firing. When a transparent pattern such as a transparent dielectric on the front plate of an AC type plasma display is required, if an inorganic component contains a filler, bubbles are generated after firing, and it does not become transparent due to light scattering by the bubbles. Therefore, a paste is not included in the inorganic component, and a paste having a low softening point glass ratio of 100% by weight must be used, so that shape retention becomes more difficult.

  Therefore, when the pattern formation is performed using a paste containing no filler in the inorganic component with a ratio of the low softening point glass in the inorganic component of 80 to 100% by weight, or the shape before firing is retained until after firing. Since it is difficult to do so, a reverse taper pattern is formed before firing as shown in FIG. 2, and if a droop due to the fluidity of the low softening point glass during firing is used, a rectangular or trapezoid pattern is formed after firing. be able to. Here, the reverse taper means a shape having a taper angle of 91 degrees to 179 degrees. The taper angle of the inversely tapered shape correlates with the film thickness of the pattern, the definition, the adhesion between the bottom and the substrate, and the like. Further, drooling due to firing is caused by the organic and inorganic ratio in the glass paste, the softening temperature of the glass fine particles, and the like, and the dripping method varies depending on the paste material. For example, it does not contain a filler like the front plate transparent dielectric paste, the organic and inorganic volume ratio is 40/60, the softening point is 350 ° C. to 550 ° C., the top width of the film after coating and drying is 100 to 200 μm, and the film thickness is In the case of 40 μm to 60 μm, by setting the reverse taper angle to 100 degrees to 135 degrees, the shape after firing at 580 ° C. is preferably a trapezoidal pattern with a taper angle of 45 degrees to 80 degrees. When the taper angle after development is 100 degrees or less, it is difficult to form a trapezoid after firing, and when it is 135 degrees or more, the bottom becomes too thin, and the pattern is peeled off.

  Examples of the method for producing the reverse taper pattern include a sand blast method, a mold transfer method, and a photolithography method. In particular, the photolithography method is suitable for patterning with a film thickness of 50 μm or less such as a transparent dielectric. Hereinafter, a method for forming a reverse taper pattern by a sandblasting method or a photolithography method will be described with reference to an AC type PDP front plate transparent dielectric pattern as an example. However, the present invention is not limited to this, and a PDP partition paste It can be preferably applied to pattern formation of pastes containing inorganic fine particles and organic components such as electrode paste and other displays.

  When using the sand blast method, first, a glass paste is applied to a glass substrate. The glass paste is not particularly limited, and examples thereof include a low softening point glass paste obtained by diluting a low softening point glass and a resin binder with a solvent so as to have a viscosity suitable for coating. Examples of the resin contained in the low softening point glass paste include cellulose resins such as ethyl cellulose. As a coating method, a coating method such as a bar coater, a roll coater, a slit die coater, a blade coater, or screen printing is used. The coating thickness can be determined in consideration of the desired height of the transparent dielectric and the shrinkage rate due to baking of the paste. Next, the coating film is dried, and a sandblast mask is formed thereon. The mask to be formed is, for example, by applying a photosensitive dry film resist on a glass paste layer and exposing and developing it, applying a photosensitive resist solution and exposing and developing it, or applying the resist solution by a method such as screen printing. Is formed. At this time, a negative resist material is more suitable as a photosensitive resist material than a positive resist material. This is because the negative resist material is generally elastic and has excellent durability during sandblasting in the subsequent process. The actinic ray used for the exposure of the photosensitive resist is most preferably an ultraviolet ray, and a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a halogen lamp or the like is used as the light source. An exposure machine using parallel rays using an ultra-high pressure mercury lamp as a light source is common.

Next, the substrate is blown and cut by sandblasting. In the sand blasting method, particles having a size of 10 to 30 μm such as calcium carbonate, silicon carbide and glass beads are preferably sprayed at a pressure of about 1.5 to 3 kg / cm ² for 15 to 30 minutes. At this time, as shown in FIG. 3, when the particles are sprayed by shifting the spray angle by 10 to 30 degrees from the vertical direction to the left and right, a reverse taper pattern can be obtained. Thereafter, the dry film of the pattern mask is removed with a peeling solution and sufficiently dried. It is preferable to use a weakly alkaline aqueous solution containing 0.1 to 1.0% by weight of sodium carbonate or the like as the peeling solution.

  When using a photolithography method, first, a photosensitive glass paste is applied to a glass substrate. As a coating method, a coating method such as a bar coater, a roll coater, a slit die coater, a blade coater, or screen printing is used. The coating thickness can be determined in consideration of the desired height of the transparent dielectric and the shrinkage rate due to baking of the paste. Next, the coating film is dried and exposed. The actinic ray used for the exposure is most preferably ultraviolet light, and as its light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp or the like is used. An exposure machine using parallel rays using an ultra-high pressure mercury lamp as a light source is common. The exposure pattern may be either a stripe pattern or a lattice pattern. Here, when the photosensitive paste coating film is exposed at the optimum exposure amount as shown in FIG. 4 and developed, a rectangular pattern can be formed, but the photosensitive paste coating film is optimal as shown in FIG. By controlling the photocuring by exposure at an exposure amount of 50% to 70% of the exposure amount, the bottom is shaved by development, and a reverse taper pattern is formed after development. The term “optimal exposure amount” as used herein means an exposure amount when the pattern after development has good adhesion between the pattern and the substrate and the pattern shape becomes rectangular. An exposure amount of 50% or less of the optimum exposure amount is not preferable because the pattern is peeled off during development due to insufficient curing. Development is usually performed by dipping, spraying, brushing, or the like. As the developer, an organic solvent in which the organic components in the photosensitive paste can be dissolved can be used. However, considering the influence on the environment, the photosensitive paste of the present invention can be used as an alkaline aqueous solution or a neutral solution. Of water. As the alkaline aqueous solution, sodium hydroxide, sodium carbonate, potassium hydroxide aqueous solution, aminoethanol aqueous solution or the like can be used.

  In the case of using a photolithography method, a reverse taper pattern can also be formed by a method using high refractive index glass as an inorganic component of the photosensitive glass paste. In other words, when the difference between the refractive index of the organic component and the refractive index of the inorganic component is 0.1 or more, as shown in FIG. It becomes insufficient. Therefore, by controlling the development time, the bottom portion that is insufficiently cured can be shaved and a reverse taper pattern can be formed. High refractive index glass refers to glass fine particles having a refractive index of 1.6 or more. If the difference in refractive index from the organic component is larger than 1.0, only the top is cured because light scattering at the top is too large. However, the pattern is easily peeled off by development. Therefore, it is preferable to use glass fine particles in which the difference in refractive index between the organic component and the inorganic component is 0.2 to 1.0. The development time can be determined by the exposure amount and the film thickness.

  As the organic component in the photosensitive glass paste of the present invention, for example, it contains a photosensitive component selected from at least one of a reactive monomer, a reactive oligomer, and a reactive polymer, and further, if necessary, a binder, photopolymerization Including additives such as initiators, ultraviolet absorbers, sensitizers, sensitizers, polymerization inhibitors, plasticizers, thickeners, antioxidants, dispersants, organic or inorganic suspending agents and leveling agents . Here, the reactivity in the reactive monomer, reactive oligomer and reactive polymer means that when the photosensitive paste is irradiated with actinic rays, the reactive monomer, reactive oligomer and reactive polymer are photocrosslinked, It means that the chemical structure changes through reactions such as polymerization, photodepolymerization, and photomodification.

  Moreover, the actinic light mentioned here refers to light in the wavelength region of 250 to 1100 nm causing such a chemical reaction, specifically, ultraviolet light such as an ultrahigh pressure mercury lamp and a metal halide lamp, visible light such as a halogen lamp, A laser beam having a specific wavelength such as a helium-cadmium laser, a helium-neon laser, an argon ion laser, a semiconductor laser, a YAG laser, and a carbon dioxide gas laser can be given.

  As the organic component used in the present invention, a compound having an ethylenically unsaturated group is preferably used. Examples of such a polymerizable monomer include a monomer having one or more photopolymerizable (meth) acrylate groups or allyl groups. Specific examples thereof include acrylic acid esters or methacrylic acid esters and carboxylic acids (eg, propionic acid acetate) of alcohols (eg, ethanol, propanol, hexanol, octanol, cyclohexanol, glycerin, trimethylolpropane, pentaerythritol, etc.). , Benzoic acid, acrylic acid, methacrylic acid, succinic acid, maleic acid, phthalic acid, tartaric acid, citric acid, etc.) and glycidyl acrylate, glycidyl methacrylate, allyl glycidyl, or tetraglycidyl methexylylene diamine, amide Derivatives (eg, acrylamide, methacrylamide, N-methylolacrylamide, methylenebisacrylamide, etc.), reaction products of epoxy compounds with acrylic acid or methacrylic acid, etc. Rukoto can. In the polyfunctional monomer, the unsaturated group may be present in a mixture of acrylic, methacrylic, vinyl, and allyl groups. These may be used alone or in combination.

  In the organic component, a polymer having an ethylenically unsaturated compound as the compound having an ethylenically unsaturated group may be used. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acrylic group, and a methacryl group.

  The polymer used as the organic component in the present invention preferably has a carboxyl group. Polymers having carboxyl groups include, for example, monomers containing carboxyl groups such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid or anhydrides thereof, and methacrylic acid esters, acrylic acid esters, It can be obtained by selecting monomers such as styrene, acrylonitrile, vinyl acetate, 2-hydroxyacrylate and copolymerizing using an initiator such as azobisisobutyronitrile.

  As the polymer having a carboxyl group, a copolymer having (meth) acrylic acid ester and (meth) acrylic acid as a copolymerization component is preferably used since the thermal decomposition temperature during firing is low. In particular, a styrene / methyl methacrylate / methacrylic acid copolymer is preferably used.

  As a method for introducing an ethylenically unsaturated bond into a side chain, an ethylenically unsaturated compound having a glycidyl group or an isocyanate group, acrylic acid chloride, methacrylic acid with respect to a mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. There is a method in which a carboxylic acid such as chloride, allyl chloride or maleic acid is reacted.

Examples of the ethylenically unsaturated compound having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, glycidyl crotonic acid, and glycidyl ether of isocrotonic acid. _{Especially, CH 2 = CCH 3 COOCH 2} CHOHCH 2 - is preferably used.

  Examples of the ethylenically unsaturated compound having an isocyanate group include (meth) acryloyl isocyanate and (meth) acryloylethyl isocyanate. In addition, the ethylenically unsaturated compound having a glycidyl group or an isocyanate group, acrylic acid chloride, methacrylic acid chloride or allyl chloride is 0.05 to 1 molar equivalent with respect to a mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. It is preferable to react.

  Preparation of an amine compound having an ethylenically unsaturated bond may be carried out by reacting glycidyl (meth) acrylate, (meth) acrylic acid chloride, (meth) acrylic anhydride, etc. having an ethylenically unsaturated bond with an amino compound. . A plurality of ethylenically unsaturated group-containing compounds may be mixed and used.

  When a binder component is required, polyvinyl alcohol, polyvinyl butyral, methacrylic acid ester polymer, acrylic acid ester polymer, acrylic acid ester-methacrylic acid ester copolymer, butyl methacrylate resin, or the like can be used as the polymer.

The resin acid value of the copolymer having a carboxyl group is preferably 50 to 150 mgKOH / g. When the acid value exceeds 150 mgKOH / g, the allowable development width becomes narrow. On the other hand, when the acid value is less than 50 mgKOH / g, the solubility of the unexposed portion in the developer is lowered. When the developer concentration is increased, the exposed portion is peeled off and it becomes difficult to obtain a high-definition pattern.
In the following, polymers suitable for water development are specifically described. In the present invention, an acrylic copolymer having an ethylenically unsaturated group and a carboxyl group at the side chain or terminal is preferably used as the polymer that can be developed with water. Such a polymer has both photocuring properties and binder properties, and an ethylenically unsaturated group is added to an acrylic copolymer formed by copolymerizing an unsaturated carboxylic acid and an ethylenically unsaturated compound. It can manufacture by adding to. Preference is given to those having an ethylenically unsaturated group and a carboxyl group in the side chain.

  Although it does not specifically limit as an ethylenically unsaturated compound polymerized as a monomer component of the acrylic copolymer which can be developed with water, Unsaturated carboxylic acid and the polyhydric alcohol and ethylenic represented by the following General formula (1) It is preferable to include a compound containing a monoester with an unsaturated carboxylic acid. In order to impart water developability to the coating film of the photosensitive glass paste, the binder polymer must have a certain level of water solubility. In order to give water solubility to the binder polymer, there is a method of introducing a hydrophilic site such as polyamide or polyether into the skeleton, but the coating film of the paste containing an inorganic component using these as a binder polymer swells, but is sufficient Since water solubility is not exhibited and a development residue remains, a good pattern cannot be obtained. Therefore, it is possible to impart sufficient water solubility to the binder polymer by introducing a water-soluble substituent such as a hydroxyl group or a carboxyl group into the side chain portion instead of the skeleton of the binder polymer.

  Also, if a paste containing a hydrophilic resin selected from polyether and polyester is used, the adhesion to the substrate will be high, and even in severe development environments such as spray development, pattern processing will be performed without peeling the exposed area. It has been known. Usually, in an extreme development environment in which a photosensitive coating film for water development is exposed and then spray development is performed using an alkaline developer, the exposed area is peeled off. If a photosensitive acrylic resin having a hydroxyl group is used, high development resistance can be obtained without adding an anti-peeling compound as a separate component, and exposure area peeling can be prevented even in a development environment using an alkaline developer. Is possible.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, 1,3-propanediol, glycerin, polyglycerin, 1,3-butanediol, 1,4-butanediol, , 2-propanediol, neopentyl glycol, pentaerythritol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, trimethylolethane, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, Examples include 2,4-pentanediol, 1,2,6-hexanetriol, cyclohexanedimethanol and the like. Examples of the ethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof. Therefore, an ester of a polyhydric alcohol and an ethylenically unsaturated carboxylic acid represents an esterified product formed by a combination of the above polyhydric alcohol compound and an ethylenically unsaturated carboxylic acid.

  In the present invention, an unsaturated acid such as an unsaturated carboxylic acid is added as a component of the copolymer in order to introduce a carboxyl group into the side chain or terminal of the acrylic copolymer. Specific examples of the carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof.

  Examples of other copolymerizable components that can be polymerized with the copolymerized component include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n- Pentyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, allyl acrylate, butoxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl acrylate, isobonyl Acrylate, 2-hydroxypropyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate Relate, stearyl acrylate, phenoxyethyl acrylate, 2-methoxyethyl acrylate, octafluoropentyl acrylate, trifluoroethyl acrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate , Thiophenol acrylate, benzyl mercaptan acrylate, a monomer in which 1 to 5 of the aromatic ring hydrogen atoms are substituted with chlorine or bromine, or styrene, p-methylstyrene, o-methylstyrene, m- Methyl styrene, chlorinated styrene, brominated styrene, α-methyl styrene, chlorinated α-methyl styrene, brominated α-methyl styrene, chloromethyl Styrene, hydroxy styrene, carboxymethyl styrene, vinyl naphthalene, vinyl anthracene, vinyl carbazole, and those that were changed to methacrylate acrylate of the above compounds. In this invention, these can be used 1 type or in combination of 2 or more types.

  As a method for introducing an ethylenically unsaturated bond into a side chain, an ethylenically unsaturated compound having a glycidyl group or an isocyanate group, acrylic acid chloride, methacrylic acid with respect to a mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. There is a method in which a carboxylic acid such as chloride, allyl chloride or maleic acid is reacted.

  Examples of the ethylenically unsaturated compound having a glycidyl group include glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, crotonic acid glycidyl ether, and isocrotonic acid glycidyl ether. In particular, glycidyl (meth) acrylate is preferably used.

  Examples of the ethylenically unsaturated compound having an isocyanate group include (meth) acryloyl isocyanate and (meth) acryloylethyl isocyanate.

  In addition, the ethylenically unsaturated compound having a glycidyl group or an isocyanate group, acrylic acid chloride, methacrylic acid chloride or allyl chloride is 0.05 to 1 molar equivalent with respect to a mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. It is preferable to make it react, More preferably, it is 0.1-0.8 molar equivalent. If the addition amount is less than 0.05 molar equivalent, the photosensitivity will be poor and pattern formation will be difficult, and if it is greater than 1 molar equivalent, the solubility of the unexposed area will decrease, which is not preferred.

  The acid value of the acrylic copolymer having an ethylenically unsaturated group and a carboxyl group at the side chain or terminal obtained by polymerizing the above components is preferably 2 to 50 mgKOH / g. More preferably, it is 5-40 mg / KOH. When the acid value exceeds 50 mgKOH / g, in the presence of glass powder containing zinc or lead, the ion crosslinking density due to the carboxyl group increases, the gelation of the paste is promoted, and the solubility of the unexposed part in the developer is increased. Causes a drop and paste pot life. On the other hand, when the acid value is 2 mgKOH / g or less, the content of the carboxyl group that affects the solubility of the unexposed area is too low, so the solubility of the unexposed area in the developing solution is remarkably lowered, and a high-definition pattern is obtained. It becomes difficult to be.

  The weight average molecular weight of the acrylic copolymer having an ethylenically unsaturated group and a carboxyl group at the side chain or terminal is preferably 5000 to 20000, more preferably 8000 to 15000. When the molecular weight is less than 5,000, the photosensitive copolymer has a weak action as a binder and the development resistance is lowered, and therefore, the exposed portion is peeled off. On the other hand, if the molecular weight is larger than 20000, the development resistance is too high, so that the solubility of the unexposed area is lowered and pattern formation becomes difficult. The photopolymerization initiator used in the present invention is selected from those generating radical species. Specific examples of the photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2- Methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 1-phenyl-1,2-propanedione-2- ( o-ethoxycarbonyl) oxime, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone -1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin iso Lopyl ether, benzoin isobutyl ether, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, alkylated benzophenone, 3,3 ' , 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-Benzoylbenzyl) trimethylammonium chloride, 2-hydroxy-3- (4-benzoylphenoxy) -N, N, N-trimethyl-1-propenaminium chloride monohydrate, 2-isopropylthioxanthone, 2,4- The Tylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2-hydroxy-3- (3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl -1-propanaminium chloride, 2,4,6-trimethylbenzoylphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2- Biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methylphenylglyoxyester, η5-cyclopentadienyl-η6-cumenyl- Iron (1 +)-hexafluorophosphate (1-), derived from diphenyl sulfide Bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 4,4-bis (dimethylamino) Benzophenone, 4,4-bis (diethylamino) benzophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 4-benzoyl-4-methylphenylketone, dibenzylketone, fluorenone, 2,3-diethoxyacetophenone, 2, 2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, benzylmethoxyethyl acetal, anthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone , Β-Chlorua Traquinone, anthrone, benzanthrone, dibenzsuberon, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2 -Phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, N-phenylglycine, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile, benzthiazole disulfide, triphenylphosphine, carbon tetrabromide, tribromophenylsulfone, benzoyl peroxide and eosin, Light reducing dyes and ascorbic acid, such as Chirenburu, a combination of a reducing agent such as triethanolamine. In the present invention, one or more of these can be used. The addition amount of the photopolymerization initiator is preferably in the range of 0.05 to 10% by weight with respect to the photosensitive organic component. More preferably, it is 0.1 to 10% by weight. When the amount of the polymerization initiator is 0.05% by weight or less, the photosensitivity becomes poor, and when the amount of the photopolymerization initiator is too large, there is a possibility that the residual ratio of the exposed portion becomes small.

  A sensitizer can be used together with a photopolymerization initiator to improve sensitivity and to expand the effective wavelength range for the reaction. Specific examples of the sensitizer include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis ( 4-dimethylaminobenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone, 4,4-bis (diethylamino) benzophenone, 4,4-bis (dimethylamino) chalcone 4,4-bis (diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4 -Dimethylaminophenylvinylene) Isonaphtho Sol, 1,3-bis (4-dimethylaminobenzal) acetone, 1,3-carbonylbis (4-diethylaminobenzal) acetone, 3,3-carbonylbis (7-diethylaminocoumarin), triethanolamine, methyl Diethanolamine, triisopropanolamine, N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl dimethylaminobenzoate, diethylamino Isoamyl benzoate, (2-dimethylamino) ethyl benzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), 2-ethylhexyl 4-dimethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazo Le, such as 1-phenyl-5-ethoxycarbonyl-thiotetrazole the like.

  It is also preferable to use a sensitizing dye. For example, coumarin dyes, ketocoumarin dyes, xanthene dyes, thioxanthene dyes, cyanine dyes, merocyanine dyes, rhodocyanine dyes, styryl dyes, base styryl dyes, rhodocyanine dyes, oxonol dyes, etc. Can be mentioned. 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 is 0.05-10 weight% normally with respect to the photosensitive organic component, More preferably, it is 0.1-10 weight%. If the amount of the sensitizer is too small, the effect of improving the photosensitivity is not exhibited, and if the amount of the sensitizer is too large, the residual ratio of the exposed portion may be reduced.

  In the present invention, it is also preferable to add an antioxidant. Antioxidants refer to those having radical chain inhibiting action, triplet elimination action, and hydroperoxide decomposition action. Since the photosensitive paste contains many glass fine particle components in a dispersed state, it is difficult to avoid light scattering inside the paste due to exposure light, and it is thought that this is caused by pattern thickening and pattern filling (residual film formation). Likely to happen. It is desirable that the pattern walls are vertically cut and rectangular. Ideally, it is soluble in the developer below a certain exposure dose, and insoluble in the developer above it. That is, it is preferable that even if cured at a low exposure amount by light scattering, it is dissolved in the developer, the pattern shape is thickened and the filling between patterns is eliminated, and the range that can be resolved even when the exposure amount is increased is wide.

  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 Salt, trimethylbenzylammonium chloride, trimethylbenzylammonium oxalate, phenyl-β-naphthylamine, parabenzylaminophenol, di-β-naphthylparaphenylenediamine, dinitrobenzene, trinitrobenzene, picric acid, quinonedioxime, Clohexanone oxime, pyrogallol, tannic acid, triethylamine hydrochloride, dimethylaniline hydrochloride, cuperone, (2,2′-thiobis (4-tert-octylphenolate) -2-ethylhexylamino nickel- (II), 4,4 '-Thiobis- (3-methyl-6-t-butylphenol), 2,2'-methylenebis- (4-methyl-6-t-butylphenol), 2,2'-thiobis- (4-methyl-6-t -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, and the like. In the present invention, these can be used alone or in combination of two or more.

  The addition amount of the antioxidant is 0.1 to 30% by weight in the photosensitive paste, and more preferably 0.5 to 20%. If it is less than these ranges, the contrast of dissolution and insolubility in the developer is small, and if this range is exceeded, the sensitivity of the photosensitive paste decreases, requiring a large amount of exposure, and the degree of polymerization does not increase and the pattern shape Cannot be maintained.

  Moreover, by adding an ultraviolet absorber, scattered light inside the paste due to exposure light can be absorbed and scattered light can be weakened. Examples of the ultraviolet absorber include benzophenone compounds, cyanoacrylate compounds, salicylic acid compounds, benzotriazole compounds, indole compounds, inorganic fine-particle metal oxides, and the like. Among these, benzophenone compounds, cyanoacrylate compounds, benzotriazole compounds, and indole compounds are particularly effective. Specific examples thereof include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-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-methyl (Chryloxy) propoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-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-chlorobenzo Triazole, 2- (2′-hydroxy-4′-n-octoxyphenyl) benzotriazole, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, 2-ethyl-2-cyano-3,3-diphenyl BONASORB UA-3901 (produced by Orient Chemical Co., Ltd.), BONASORB U, which is an acrylate and indole-based absorbent A-3902 (manufactured by Orient Chemical Co., Ltd.) SOM-2-0008 (manufactured by Orient Chemical Co., Ltd.) and the like are exemplified, but not limited thereto. Furthermore, a methacryl group or the like may be introduced into the skeleton of these ultraviolet absorbers and used as a reaction type. In the present invention, one or more of these can be used.

  The amount of the UV absorber added is in the range of 0.001 to 10% by weight, more preferably 0.005 to 5% in the paste. Beyond these ranges, the transmission limit wavelength and the wavelength gradient width change, so that the ability to absorb scattered light is insufficient, the transmittance of exposure light is lowered, and the sensitivity of the photosensitive paste is lowered.

  In the present invention, an organic dye can be added as a mark for exposure and development. By adding a dye and coloring it, the visibility is improved, and it becomes easy to distinguish the portion where the paste remains during development and the portion where it has been removed. Although it does not specifically limit as organic dye, The thing which does not remain in the insulating film after baking is preferable. Specifically, anthraquinone dyes, indigoid dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes, phthalimide dyes Dyes and perinone dyes can be used. In particular, it is preferable to select one that absorbs light having a wavelength in the vicinity of h-line and i-line, for example, a carbonium dye such as basic blue. The amount of organic dye added is preferably 0.001 to 1% by weight.

  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. As an organic solvent used at this time, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, bromobenzene, Chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, and the like, and organic solvent mixtures containing one or more of these are used.

  As the glass fine particles, it is preferable to contain low softening point glass having a glass transition point of 350 to 550 ° C. in the paste. Usually, the dielectric or barrier rib paste is fired at 430 ° C. to 650 ° C. after the pattern is formed. Therefore, if the glass transition point is less than 350 ° C., the flowability of the glass during firing is too high, and the pattern shape is lost. If the glass transition point is 550 ° C. or higher, the glass powder does not sinter, and thus it does not become transparent. More preferably, it is 400 degreeC-530 degreeC.

  In this invention, it is preferable to contain the low softening point glass whose said glass transition point is 350-550 degreeC in the range of 50-90 weight% in a paste. When there is too little content of glass powder, the shrinkage | contraction of the pattern by baking will become large and a shape will become defect. On the other hand, if the amount is too large, the photosensitive property of the paste is deteriorated, so that pattern formation becomes difficult. More preferably, it is 60 to 80% by weight.

  Moreover, it is preferable that the refractive index of glass microparticles exists in the range of 1.5-1.65. By using glass fine particles formed by mixing metal oxide so that the refractive index is 1.5 to 1.65, by matching the refractive index of the glass powder and the photosensitive organic component, and suppressing light scattering High-precision pattern processing tends to be possible. For example, a glass powder composed of silicon oxide: 22, aluminum oxide: 23, boron oxide: 33, lithium oxide: 9, magnesium oxide: 7, barium oxide: 4 and zinc oxide 2 (% by weight) has a glass transition point of 490. C., softening point: 528.degree. C. and refractive index at g-line wavelength (436 nm): 1.59, and can be preferably used as the glass fine particles of the present invention. More preferably, it is in the range of 1.53 to 1.62.

  The low softening point glass that can be preferably used as the glass fine particles used in the photosensitive paste of the present invention has, for example, the following composition (as oxide).

Lithium oxide, sodium oxide, potassium oxide
3-15% by weight
5-30% by weight of silicon oxide
Boron oxide 20-45% by weight
Barium oxide or strontium oxide
2 to 15% by weight
Aluminum oxide 10-25% by weight
Magnesium oxide or calcium oxide
2 to 15% by weight
As described above, at least one of alkali metal oxides of lithium oxide, sodium oxide or potassium oxide is used, and the total amount is preferably 3 to 15% by weight, more preferably 3 to 10% by weight.

  Alkali metal oxides not only facilitate the control of the softening point and thermal expansion coefficient of glass, but also can reduce the refractive index of glass, thereby reducing the difference in refractive index from the photosensitive organic component. It becomes easy. By making the total amount of alkali metal oxides 3% by weight or more, the effect of lowering the softening point of the glass can be obtained, and by making it 15% by weight or less, the chemical stability of the glass is maintained and thermal expansion is achieved. The coefficient can be kept small. As the alkali metal, lithium is preferably selected in consideration of lowering the refractive index of the glass and preventing ion migration.

  The blending amount of silicon oxide is preferably 5 to 30% by weight, more preferably 10 to 30% by weight. Silicon oxide is effective in improving the denseness, strength and stability of glass, and is effective in lowering the refractive index of glass. The thermal expansion coefficient can be controlled to prevent peeling due to mismatch with the glass substrate. By setting the content to 5% by weight or more, the thermal expansion coefficient is kept small, and no cracks occur when baked on a glass substrate. Further, the refractive index can be kept low. By setting it to 30% by weight or less, the glass transition point and the softening point can be kept low, and the baking temperature on the glass substrate can be lowered.

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

  It is preferable that at least one of barium oxide and strontium oxide is used, and the total amount is 2 to 15% by weight, more preferably 2 to 10% by weight. These components are effective in adjusting the thermal expansion coefficient, and are preferable in terms of application of the baking temperature to the heat resistance of the substrate, electrical insulation, stability of the partition walls formed, and denseness. By setting the content to 2% by weight or more, devitrification due to crystallization can be prevented. Moreover, by setting it as 15 weight% or less, a thermal expansion coefficient can be restrained small and a refractive index can also be restrained small. Also, the chemical stability of the glass can be maintained.

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

  Furthermore, it is preferable that calcium oxide and magnesium oxide are blended for facilitating melting of the glass and controlling the thermal expansion coefficient. Calcium oxide and magnesium oxide are preferably blended in a total of 2 to 15% by weight. When the total amount is 2% by weight or more, devitrification of the glass due to crystallization can be prevented, and when the total amount is 15% by weight or less, 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 and aluminum oxide are mixed so as to have a predetermined composition, melted at 900 to 1200 ° C., and then rapidly cooled. A glass frit is 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, it is possible to use ultra-pure alkoxides of 99.99% or higher and organic metal raw materials, and to use powders that are homogenized by the sol-gel method. This is preferable because a high-strength insulating layer with few pores can be obtained.

The particle diameter of the glass powder used in the above is selected in consideration of the shape of the pattern to be produced. The powder has a 50% by weight particle diameter (average particle diameter) of 2 to 3.5 μm and a top size of 15 μm or less. It is preferable that Further, it is preferable that the 10% by weight particle diameter is 0.6 to 1.5 μm, the 90% by weight particle diameter is 4 to 8 μm, and the specific surface area is 1.5 to ^2.5 m ² / g. More preferably, the average particle size is 2.5 to 3.5 μm and the specific surface area is 1.7 to 2.4 m ² / g. Within this range, light can be sufficiently transmitted at the time of ultraviolet exposure, and a barrier rib pattern having a small line width difference between the upper and lower sides can be obtained. When the average particle size is 2.0 μm or less and the specific surface area exceeds 2.5 m ² / g, the powder becomes too fine and light is scattered during exposure to cure the unexposed portion, which is not preferable.

  Further, the low softening point glass that can be preferably used as the inorganic fine particles of the photosensitive paste used for the transparent dielectric pattern on the front plate is preferably one that exhibits transparency after firing, and a known glass insulating material can be applied. Examples thereof include glass, bismuth borosilicate, and zinc borosilicate.

Therefore, the glass powder is PbO 0-80% by weight in terms of oxide.
BiO ₂ 0-80% by weight
ZnO 0-80% by weight
As a glass forming component other than those described above, B ₂ O ₃ 2 to 40% by weight
SiO ₂ 2-30% by weight
BaO 1-30% by weight
It is preferable to contain what consists of these composition ranges. If it is this range, a glass transition temperature is 350-550 degreeC, and the glass powder with a high visible light transmittance | permeability is obtained after baking.

Among the glass components, PbO, BiO ₂ , and ZnO are components that lower the glass softening point, and in the present invention, any one of them must be contained, and the content thereof is 40 to 80 in total. It is preferable that it is weight%. If it is less than 40% by weight, the glass transition temperature becomes 550 ° C. or higher, and firing becomes difficult. If the content is more than 80% by weight, vitrification becomes difficult and the coefficient of thermal expansion increases, which may cause cracks during firing. A more preferable content is 50 to 75% by weight in total.

B ₂ O ₃ is a component that stabilizes the glass and increases the fluidity during firing. It is also effective for lowering the refractive index, and it is preferably blended in the range of 2 to 40% by weight, more preferably 5 to 30% by weight. By setting it to 2% by weight or more, the glass transition point and the load softening point are kept low, and baking onto the glass substrate is facilitated. Moreover, the chemical stability of glass can be maintained by setting it as 40 weight% or less.

SiO ₂ is effective in improving the denseness, strength and stability of the glass, and is effective in reducing the refractive index of the glass. The blending amount is preferably 2 to 30% by weight. By making it 2% by weight or more, the thermal expansion coefficient is kept small, and cracks do not occur when baked on a glass substrate. By setting it to 30% by weight or less, the glass transition point and the softening point can be kept low, and the baking temperature on the glass substrate can be lowered.

  BaO is an effective component for widening the vitrification range. Moreover, it is effective in adjusting the thermal expansion coefficient, and is preferable in terms of application of the baking temperature to the heat resistance of the substrate, electrical insulation, stability of the dielectric pattern to be formed and denseness, and is 1 to 30% by weight. It is preferable to mix in a range. More preferably, it is 2 to 25% by weight or less. By setting the content to 1% by weight or more, devitrification due to crystallization can be prevented. Moreover, by setting it as 30 weight% or less, a thermal expansion coefficient can be restrained small and a refractive index can also be restrained small. Also, the chemical stability of the glass can be maintained.

Further, _Li 2 O as a component other than the above may contain with at least one of alkali metal oxides Na ₂ O and _{K 2} O. When contained, the total amount is preferably 25% by weight or less. Alkali metal oxide not only facilitates control of the glass load softening point and thermal expansion coefficient, but also reduces the refractive index of the glass, thus reducing the refractive index difference from the photosensitive organic component. Becomes easier. When the total amount of alkali metal oxides is 25% by weight or less, the chemical stability of the glass can be maintained and the thermal expansion coefficient can be kept small. As the alkali metal, lithium is preferably selected in consideration of lowering the refractive index of the glass and preventing ion migration.

In addition to the above components, in order to adjust the softening point, thermal expansion coefficient, transparency, stability, weather resistance, etc. of the low softening point glass, CaO, MgO, SrO, Al ₂ O ₃ , TiO ₂ , ZrO ₂ , CeO ₂ , CuO or the like may be appropriately blended. If these components are added too much, the stability of the glass is impaired, so the total amount is preferably 10% by weight or less. For example, from SiO ₂ : 11.3, B ₂ O ₃ : 33.8, ZnO: 40.2, Na ₂ O: 2.2, K ₂ O: 12.0, CuO: 0.5 (% by weight) The resulting glass fine particles exhibit a glass transition point: 459 ° C., a softening point: 561 ° C., and a refractive index: 1.84. This glass fine particle has characteristics such as high transparency after sintering in a sintering temperature range of 570 ° C. to 590 ° C. (total light transmittance of 80% or more at a film thickness of 20 μm) and excellent migration prevention. And it can be used more preferably.

As the filler, high softening point glass or oxide can be used. The filler also preferably has a refractive index in the range of 1.5 to 1.65 in order to match the refractive index of the photosensitive organic component in the photosensitive paste and to suppress exposure light scattering. High softening point glass, cordierite (2MgO · 2Al ₂ O ₃ · 5SiO ₂ ), Celsian (BaO · Al ₂ O ₃ · SiO ₂ ) whose composition is adjusted so that the refractive index of the filler is within the above range. , Anorthite (CaO · Al ₂ O ₃ · 2SiO ₂ ), steatite (MgO—SiO ₂ ), spodumene (LiO ₂ · Al ₂ O ₃ · 4SiO ₂ ) and forsterite (2MgO · SiO ₂ ), silicon oxide, Aluminum oxide, titanium oxide, zirconium oxide, yttrium oxide, cerium oxide, magnesium oxide, zinc oxide, manganese oxide, copper oxide, iron oxide, holmium oxide, lead oxide, and tin oxide can be used. As a high softening point glass, what has a glass transition point of 500-1200 degreeC and a load softening point of 550-1200 degreeC is preferable. Although the composition of high softening point glass is not limited to this, For example, the thing of the following oxide conversion compositions can be used.

Silicon oxide 15-50% by weight
Boron oxide 5-20% by weight
Barium oxide 2-10% by weight
Aluminum oxide 15-50% by weight.

  More specifically, for example, 38% by weight of silicon oxide, 10% by weight of boron oxide, 5% by weight of barium oxide, 36% by weight of aluminum oxide, and other components containing calcium oxide, zinc oxide, and magnesium oxide in small amounts. The refractive index of the high softening point glass having a glass transition point of 625 ° C. and a softening point of 750 ° C. is 1.59, which is equivalent to the refractive index of the low softening point glass preferably used in the present invention.

  Moreover, it is also preferable to contain magnesium oxide as a filler in terms of contributing to discharge stability.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to this. In the examples, the concentration (%) is% by weight unless otherwise specified. First, a refractive index measurement, a glass softening point measurement, and a pattern shape evaluation method will be described.
(Refractive index measurement)
The refractive index of the organic component was measured with respect to light having a wavelength of 436 nm at 25 ° C. by an ellipsometry method after adjusting the organic component in the paste and applying and drying steps. The refractive index of the glass was measured by a liquid immersion method. The glass particles were immersed in several refractive index immersion liquids, and the refractive index of the immersion liquid when the Becke line generated at the boundary between the particles and the immersion liquid disappeared with an optical microscope was defined as the refractive index of the glass.
(Measurement of glass softening point)
Glass was sealed in a sample holder, and the temperature was raised from 30 ° C. to 700 ° C. at 10 ° C./min using a differential scanning calorimeter (“DSC-600E” manufactured by Shimadzu Corporation). The temperature at the peak top of the obtained endothermic peak was defined as the glass softening point.
(Evaluation of pattern shape)
The substrate was cut into small pieces, and a cross section perpendicular to the longitudinal direction of the stripe pattern was observed with a scanning electron microscope (Hitachi, Ltd. S2400).
(Paste preparation method)
Each component of the organic component was mixed and dissolved, then glass fine particles were added and kneaded with three rollers to prepare a paste composed of the glass fine particles and the organic component. The paste was defoamed with a centrifugal defoamer.

  Table 1 shows the composition of the glass particles 1 and 2 and the filler used, and Table 2 shows the composition of the organic components 1 and 2. The details of the organic components in Table 2 are as follows.

Polymer 1: 0.4-equivalent methyl glycidyl methacrylate added to the carboxyl group of a copolymer of methacrylic acid / methyl methacrylate / styrene = 40/30/30 (weight average molecular weight 43,000, acid Value 100).
Polymer 2: Ethyl cellulose Polymer 3: Photosensitive acrylic system obtained by addition reaction of 0.9 molar equivalent of glycidyl methacrylate to the carboxyl group of a copolymer consisting of 30% acrylic acid, 40% methyl methacrylate and 30% glycerin monoacrylate Polymer. Acid value 10 mgKOH / g, weight average molecular weight 9000.
Monomer: Dipentaerythritol hexaacrylate IC 369: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1
Sudan: Azo-based red dye, C ₂₄ H ₂₀ N ₄ O
γ-BL: γ-butyrolactone (Example 1)
The paste P1 was applied on a 5 inch square glass substrate (PD-200; manufactured by Asahi Glass Co., Ltd.) to a coating thickness of 90 μm using a slit die coater, and then dried at 70 ° C. for 30 minutes. . The coating thickness after drying was 50 μm.

Next, exposure was performed through a photomask. A stripe pattern emulsion mask was used as the photomask. At this time, in order to prevent the mask from being contaminated, a gap of 100 μm was provided between the mask and the coating surface. The exposure was performed by ultraviolet exposure at 400 mJ / cm ² . Thereafter, development was performed by applying pure water having a pH of 7.0 maintained at 35 ° C. for 30 seconds in a shower, and a portion not photocured was removed to form a pattern on the glass substrate.

  Pattern processing was performed with a paste using glass fine particles A1 having a high refractive index so that light scattering at the top portion was increased, and a reverse taper pattern having a taper angle of 135 degrees after development was obtained.

Further, the obtained glass substrate was dried at 80 ° C. for 5 minutes, and then fired at a maximum temperature of 580 ° C. (maximum temperature holding time of 15 minutes). Since the filler was not included, a reverse taper shape was obtained during firing, and a trapezoidal pattern having a taper angle of 60 degrees after firing was obtained.
(Example 2)
A pattern was formed in the same manner as in Example 1 except that the paste P2 was used, the exposure amount of ultraviolet exposure was 200 mJ / cm ² , and the development time was 10 seconds. Photocuring was controlled with an exposure amount of ultraviolet exposure lower than the optimum exposure amount (400 mJ / cm ² ), and the bottom was shaved by development to obtain a reverse taper pattern with a taper angle of 130 degrees. After firing, a trapezoidal pattern with a taper angle of 50 degrees was obtained.
(Comparative Example 1)
A pattern was formed in the same manner as in Example 2 except that the exposure amount of ultraviolet exposure was 400 mJ / cm ² and the development time was 15 seconds. After development, it became a rectangular pattern with a taper angle of 85 degrees, and after baking, it became a defective pattern.
(Example 3)
The paste P3 was applied on a 5-inch square glass substrate (PD-200; manufactured by Asahi Glass Co., Ltd.) to a coating thickness of 90 μm using a slit die coater, and then dried at 70 ° C. for 30 minutes. . The coating thickness after drying was 50 μm.

  A dry film negative photosensitive resist material was pressure-bonded thereon at a temperature of about 80 to 100 ° C. using a laminator, and pattern exposure and development treatment were performed to form a sandblast mask.

  Next, the substrate was blown and cut by a sandblast method. Thereafter, the dry film of the pattern mask was removed with a peeling solution and sufficiently dried. During sandblasting, the angle was shifted 30 degrees from the vertical direction to the left and right, and the powder was sprayed to obtain a reverse taper pattern with a taper angle of 120 degrees.

Further, the obtained glass substrate was fired at a maximum temperature of 580 ° C. (maximum temperature holding time of 15 minutes). Since the filler was not included, a reverse tapered shape was formed during firing, and a trapezoidal pattern having a taper angle of 45 degrees was obtained. However, since the number of processes is increased as compared with Examples 1 and 2, the productivity is poor.
Example 4
A pattern was formed in the same manner as in Example 3 except that the paste P4 having a weight ratio of glass fine particles A2 and filler of 80:20 was used and that the sandblasting spray angle was 10 degrees. After sandblasting, an inverted taper shape with a taper angle of 100 degrees was obtained, and after firing, a trapezoidal shape with a taper angle of 80 degrees was obtained. Since the filler was included, who was smaller than Examples 1-3.
(Example 5)
A pattern was formed in the same manner as in Example 4 except that paste P5 having a ratio of glass fine particles A2 to filler of 90:10 in terms of% by weight was used. After sandblasting, an inverted taper shape with a taper angle of 100 degrees was obtained, and after firing, a trapezoidal shape with a taper angle of 65 degrees was obtained. Since the amount of filler was less than in Example 4, the amount of filler was greater than in Example 4.
(Comparative Example 2)
A pattern was formed in the same manner as in Example 4 except that paste P6 in which the ratio of glass fine particles A2 to filler was 70% by weight was used. Since the ratio of the filler was large, firing was insufficient, and an inverted taper shape having a taper angle of 100 degrees was maintained.

  Table 3 shows the glass fine particles and organic components of the pastes used in Examples 1 to 5 and Comparative Examples 1 and 2, and Table 4 shows the results.

(Example 6)
The paste P4 was applied on a 5-inch square glass substrate (PD-200; manufactured by Asahi Glass Co., Ltd.) using a slit die coater to a coating thickness of 300 μm, and then dried at 100 ° C. for 90 minutes. . The coating thickness after drying was 180 μm.

  A dry film negative photosensitive resist material was pressure-bonded thereon at a temperature of about 80 to 100 ° C. using a laminator, and pattern exposure and development treatment were performed to form a sandblast mask.

  Next, the substrate was blown and cut by a sandblast method. Thereafter, the dry film of the pattern mask was removed with a peeling solution and sufficiently dried. When sandblasting, the powder was sprayed by shifting the angle from the vertical direction to the left and right by 10 degrees to obtain a reverse taper pattern with a taper angle of 100 degrees.

Furthermore, the obtained glass substrate was fired at a maximum temperature of 580 ° C. (maximum temperature holding time of 15 minutes), and a trapezoidal shape having a taper angle of 80 degrees was obtained after baking.

(Example 7)
A back plate of an AC (alternating current) type plasma display panel was formed using a glass substrate having a size of 340 × 260 × 2.8 mm (“PD-200” manufactured by Asahi Glass Co., Ltd.).

  A striped electrode having a pitch of 140 μm, a line width of 60 μm, a thickness of 4 μm after firing, and a dielectric layer having a thickness of 10 μm were formed on the substrate. Next, a barrier rib pattern was formed in the same manner as in Example 5.

  The phosphor paste was applied between the barrier ribs by screen printing, but the screen plate other than the fiber waste was not clogged, and it could be produced stably and continuously. The direct coating method was able to produce a stable production as well. Then, it dried and baked (500 degreeC, 30 minutes), and formed the fluorescent substance layer in the side and bottom part of a partition.

A front glass substrate was prepared and bonded and sealed to the back glass substrate, and then a discharge gas was sealed, and a driving circuit was joined to prepare a PDP. A voltage was applied to this panel to observe the display. Those using any of the pastes in Table 1 had a bright brightness and a good display free from display defects.
(Example 8)
A pattern was formed in the same manner as in Example 1 except that the paste P7 was used and the development time was 15 seconds. A reverse taper pattern with a taper angle of 135 degrees was obtained. After firing, a trapezoidal pattern with a taper angle of 60 degrees was obtained.
Example 9
A pattern was prepared in the same manner as in Example 8 except that the paste P8 was used. A reverse taper pattern having a taper angle of 130 degrees was obtained. After firing, a trapezoidal pattern with a taper angle of 65 degrees was obtained.

It is a figure which shows a taper angle. It is a figure which becomes trapezoid shape after baking from reverse taper shape. It is a figure which performs sandblasting to a coating film. It is a figure which exposes a coating film by optimal exposure amount, and forms a rectangular pattern after image development. It is a figure which exposes a coating film by 50 to 70% of optimal exposure amount, and forms a reverse taper pattern after image development. It is a figure which forms the reverse taper pattern by exposing and developing the coating film containing the glass fine particle of high refractive index.

Explanation of symbols

1: Pattern 2: Reverse taper pattern
3: Substrate 4: Trapezoid pattern 5: Spraying sandblast 6: Sandblast mask 7: Paste coating film 8: Exposure mask 9: Exposure light 10: Exposure part 11: Developer

Claims (5)

In a pattern forming method in which a paste containing inorganic fine particles and an organic component is applied, baked after forming a pattern, 80 to 100% by weight of glass fine particles having a glass softening point of 350 ° C. to 550 ° C. and 0% filler as inorganic fine particles A pattern forming method, wherein a paste containing ˜20% by weight is applied, and thereafter a pattern is formed in a reverse taper shape, followed by baking to form a rectangular or trapezoidal pattern. 2. The pattern forming method according to claim 1, wherein the pattern forming method is a photolithography method. 3. The pattern forming method according to claim 1, wherein the difference between the refractive index of the organic component of the paste and the refractive index of the glass fine particles is larger than 0.1. A method for producing a plasma display member, wherein the pattern forming method according to claim 1 is used. A method for manufacturing a plasma display, wherein the method for manufacturing a plasma display member according to claim 4 is used.

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