KR20130139320A - Paste composition, and method for producing plasma display - Google Patents

Abstract

After pattern-processing the paste which consists of an organic substance and water, an organic substance can be distilled off by combustion or decomposition by a high temperature baking process, and a pattern by an inorganic material can be formed by partially melting and sintering glass. In this method, there is a problem in that stress is applied when the organic component is removed by firing, and pattern defects are likely to occur. As a paste composition containing a glass powder and an organic component, the viscosity η 1 (dPa · s) at 570 ° C. and the viscosity η 2 (dPa · s) at 590 ° C. as a glass powder satisfy the following formula (1): It is set as the paste composition characterized by containing 40 mass% or more of melting | fusing point glass powder with respect to all the glass powder. 0.5 <log (eta) 1-log (eta) 2 <0.9 (1) This paste composition can form the pattern which interrupted the pattern defect.

Description

Paste composition and manufacturing method of plasma display {PASTE COMPOSITION, AND METHOD FOR PRODUCING PLASMA DISPLAY}

The present invention relates to a paste composition. In particular, it is related with the manufacturing method of the paste suitable for formation of the insulating pattern used for flat panel displays, such as a plasma display panel, a field emission display, a fluorescent display tube, and a panel for flat panel displays.

In recent years, development of flat panel displays, such as a plasma display panel, a field emission display, a fluorescent display tube, a liquid crystal display device, an electroluminescence display, and a light emitting diode, is progressing rapidly. Among them, the plasma display generates a plasma discharge between the opposing electrodes in the discharge space formed between the front glass substrate and the back glass substrate, and displays the fluorescent substance provided in the discharge space by irradiating ultraviolet rays generated from the gas enclosed in the discharge space. To do. Gas discharge type displays such as plasma displays and fluorescent display tubes require an insulating partition for partitioning the discharge space. In addition, field emission displays, such as field emission displays, require insulating barriers to repel gate electrodes and cathodes.

As a method of forming these barrier ribs, the barrier paste is repeatedly applied and patterned by a screen printing plate, dried, and then screened by baking, masked with a resist on a layer of the dried barrier material, and then shaved by sandblasting. After baking the sand blast method which bakes, the dried partition material, the mask is masked with a resist on the layer, and the etching method (patent document 1) which etches and presses the metal mold | die which has a pattern to the coating film of a partition paste, and patterns After forming the film, the photosensitive paste method of baking is applied after the mold transfer method (imprint method) (patent document 4) which performs baking, the partition material which consists of the photosensitive paste material, and it performs exposure and image development, and is baked. Lithographic methods) and the like (Patent Documents 2 and 5). Common to these methods is to form a paste coating film pattern using a paste made of an organic material and an inorganic material, and then, after the organic material is distilled off by combustion or decomposition by a high temperature baking process, the glass is partially melted and sintered to form an inorganic material. It is the point which forms the pattern by. When using a glass substrate as a base material, it is common to make baking temperature 650 degrees C or less in order to suppress deformation of a glass substrate. However, in the above method, there is a problem in that stress is applied when the organic component is removed by firing, and pattern defects are likely to occur.

Here, the cause of the pattern defect is a plastic stress when the first organic material is calcined and distilled off at a high temperature, and a shrinkage stress when the glass component is softened and contracted at a second high temperature. As a method of inhibiting pattern defects caused by first plastic stress, Patent Document 3 proposes a method of inhibiting pattern defects by increasing the strength of a pattern against stress by adding a urethane compound having excellent flexibility in an organic component. This method is effective to prevent defects caused by stress generated in the process of decomposing organic matters during firing, but pattern defects caused by shrinkage stress in the sintering process of glass components after organic matters are removed by firing. There is no effect to suppress.

Japanese Patent Laid-Open No. 7-320641 Japanese Patent Laid-Open No. 9-310030 Japanese Patent Publication No. 2002-173597 Japanese Patent Publication No. 2009-203356 United States Patent 6197480

Therefore, the present invention provides a paste capable of suppressing pattern defects generated when the inorganic material is sintered by controlling the viscosity characteristics at a high temperature of the glass material, in particular, by designing an amount of change in viscosity with respect to a temperature within a certain range.

In order to solve the said subject, this invention has the following structures.

(1) A paste composition comprising a glass powder and an organic component, wherein the viscosity η 1 (dPa · s) at 570 ° C. and the viscosity η 2 (dPa · s) at 590 ° C. satisfy the following formula (1): A paste composition comprising a melting point glass powder based on 40% by mass or more of the total glass powder.

0.5 <logη1-logη2 <0.9 (1)

(2) As a paste composition containing a glass powder and an organic component, the viscosity η 1 (dPa · s) at 570 ° C. and the viscosity η 2 (dPa · s) at 590 ° C. satisfy the following formula (2) as the glass powder: The paste composition characterized by containing 40 mass% or more of low-melting-point glass powder with respect to all the glass powder.

1.05 <logη1 / logη2 <1.11 (2)

(3) The paste composition according to (1) or (2), wherein η1 (dPa · s) and η2 (dPa · s) satisfy the following formulas (3) and (4).

8.5 <logη1 <9.0 (3)

7.8 <logη2 <8.5 (4)

(4) The paste composition according to any one of (1) to (3), wherein the softening temperature of the low melting glass powder is 560 to 610 ° C.

5 (1) - to the method according to any one of the low-melting alkali metal oxide content of the glass powder X (M ₂ O) (weight%) and zinc oxide content X (ZnO) (mass%) of 4 Satisfying formula (5), and furthermore, silicon oxide content X (SiO ₂ ) (mass%), aluminum oxide content X (Al ₂ O ₃ ) (mass%) and boron oxide content X (B) in the low melting point glass powder. ₂ O ₃ ) (mass%) satisfies the following formula (6), and the content X (M ₂ O) of the alkali metal oxide in the low-melting-point glass powder is in the range of 4-10 mass%, and zinc oxide Content X (ZnO) of is in the range of 3-10 mass%, The paste composition characterized by the above-mentioned.

1.0≤X (M ₂ O) / X (ZnO) ≤3.0 (5)

1.5 <(X (SiO ₂ ) + X (Al ₂ O ₃ )) / X (B ₂ O ₃ ) <2.0 (6)

(6) The paste composition according to any one of (1) to (5), comprising a photoreactive material as an organic component.

(7) A method of manufacturing a plasma display, wherein the partition wall is formed using the paste composition of the above (1) to (6).

(Effects of the Invention)

According to the paste of the present invention, an inorganic pattern free of defects can be obtained after firing, and in particular, a display member free of defects in the pattern can be provided, and is effective for producing a high yield of PDP at low cost.

The paste of the present invention is composed of organic matter and inorganic powder. A certain amount of organic matter is required in order to form a pattern before firing. However, when the organic component is too large, the amount of the substance removed in the firing process increases, and the plastic shrinkage rate increases, which is likely to cause pattern defects in the firing process. In addition, organic matters tend to remain in the firing step, and the remaining organic matters tend to cause contamination in the display. On the other hand, when the organic component becomes too small, not only the mixing and dispersion of the inorganic fine particles in the paste will be insufficient, but also the problems such as a decrease in the applicability of the paste due to an increase in the viscosity of the paste will adversely affect the stability of the paste. There is a case. In addition, since the dispersibility of the organic component and the inorganic fine particles is lowered, defects tend to occur during firing. Therefore, it is preferable that content of the inorganic fine particle in a paste is 40 mass%-80 mass%, More preferably, it is 40 mass%-70 mass%.

In the present invention, in order to remove the organic material almost completely by firing and to secure a constant strength, it is preferable to use a glass powder having a softening temperature of 480 ° C or higher as the low melting point glass powder to be used. If the softening temperature is 480 ° C. or lower, the glass is softened before the organic component is sufficiently removed at the time of firing, and the residue of the organic substance is introduced into the glass. In this case, there is a fear that organic substances are gradually released in the future, thereby degrading product quality. Therefore, it is preferable to form an inorganic pattern by carrying out sintering of a glass component, after forming a paste using the glass powder of 480 degreeC or more softening temperature, heating to 500 degreeC or more and completely removing an organic substance. Moreover, when baking temperature becomes 620 degreeC or more, since a deformation becomes large in a general glass substrate, 620 degreeC or less is preferable as baking temperature. That is, it is preferable to bake at 500-620 degreeC for formation of the inorganic material pattern in a display, and it is preferable to use the glass of the softening temperature of 480-620 degreeC as a characteristic of the low melting-point glass powder in the paste used at this time. . In addition, in the baking process, when the viscosity change with respect to the temperature of glass powder is large, plastic shrinkage in a short time tends to occur, and instantaneous shrinkage stress tends to be large, leading to pattern defects. Therefore, by making the viscosity change of the low-melting-point glass powder in this high temperature region constant, it is possible to make plastic shrinkage relieve and to hardly generate pattern defects due to shrinkage stress. In particular, it is important to suppress the viscosity fluctuation in the range of 570-590 degreeC below a fixed level. That is, the paste hardly generate | occur | produces a pattern defect by using the low melting glass powder in which viscosity (eta) 1 (dPa * s) in 570 degreeC and viscosity (eta2 (dPa * s) in 590 degreeC satisfy | fill following formula (1). You can write

0.5 <logη1-logη2 <0.9 (1)

In this invention, the viscosity (eta) 1 (dPa * s) at 570 degreeC and the viscosity (eta2) (dPa * s) at 590 degreeC of low softening point glass can be measured using the penetration method mentioned later.

If the value of logη1-logη2 is 0.5 or less, it becomes difficult to fully advance softening by heating. That is, in the low softening point glass sintered by heating, logη1-logη2 generally becomes larger than 0.5. In addition, in the case of 0.9 or more, the viscosity change with respect to temperature is large, and a pattern defect by a temporary shrinkage stress is easy to generate | occur | produce.

Moreover, the viscosity which is hard to produce a pattern defect is produced by using the glass powder whose viscosity (eta) 1 (dPa * s) in 570 degreeC and viscosity (eta2 (dPa * s) in 590 degreeC satisfy | fill the following formula (2). Can be.

1.05 <logη1 / logη2 <1.11 (2)

When the value of log? 1-log? 2 is 1.05 or less, it is difficult to sufficiently advance the softening by heating, and when it is 1.11 or more, the viscosity change with respect to temperature is large, and it is easy to show a pattern defect due to the shrinkage stress caused by the temperature change in a short time.

As a low melting-point glass powder used for the paste composition of this invention, when softening temperature is 560-610 degreeC, suitable sintering advances and the inorganic pattern excellent in intensity | strength can be formed.

The softening temperature according to the present invention can usually be measured by using a differential thermal analysis device (DTA), and for example, the endothermic end temperature in the endothermic peak from the DTA curve obtained by measuring the glass powder by the tangential method. Can be extrapolated.

It is necessary for the content rate of the low melting glass contained in the paste composition of this invention to be 40 mass% or more with respect to all glass powder from a sinterability point.

In addition, by forming the viscosity η 1 (dPa · s) at 570 ° C. and the viscosity η 2 (dPa · s) at 590 ° C. of the glass powder used herein, a dense and excellent inorganic pattern can be formed. have. That is, by containing 40 mass% or more of low melting-point glass powder which has a relationship of following formula (3) and (4), the inorganic pattern which is more excellent in strength after baking can be formed.

8.5 <logη1 <9.0 (3)

7.8 <logη2 <8.5 (4)

It is preferable to design so that log (eta) 1 and log (eta) 2 may satisfy | fill said Formula (3) and Formula (4) in order to advance sintering of glass by advancing sintering of a certain grade. If logeta1 or logeta2 is too large, sintering will not progress easily and the strength of a formed object may run short. On the other hand, when log (eta) 1 or log (eta) 2 is too small, pattern shape may deform | transform with glass sintering, and shape maintenance may become difficult. That is, by setting it as the range which satisfy | fills the said formula, especially suitable sintering property can be obtained and the inorganic pattern without a defect can be obtained. The low softening point glass powder included in the paste composition of the present invention may use oxides of lead oxide, bismuth oxide, zinc oxide, and alkali metal which are effective materials for low melting point of the glass, but lead oxide is not preferable in the environment. Bismuth oxide is disadvantageous in that it uses bismuth which is an expensive element. Therefore, it is preferable to adjust the softening temperature of glass using an alkali metal oxide. In addition, although alkali metal generally refers to lithium, sodium, potassium, rubidium, and cesium, alkali metal oxide contained as a component of the low softening point glass powder of this invention refers to lithium oxide, sodium oxide, and potassium oxide, and to the total content of oxide lithium, sodium and potassium oxide, X (M ₂ O).

The content X (M ₂ O) of the alkali metal oxide in this case is preferably in the range of 4 to 10% by weight of the total glass. If it is less than 4 mass%, in order to bake on a glass substrate, sufficient softening temperature reduction may not be possible. Moreover, when more than 10 mass%, the viscosity in high temperature may fall too much. Moreover, only the softening temperature adjustment by an alkali metal will fall too much the viscosity in high temperature. Therefore, it is preferable to add 3-10 mass% of zinc oxides. If it is less than 3 mass%, the viscosity in high temperature will become high, and when there is more than 10 mass%, there exists a tendency for the cost of glass to become high. In particular, it is preferable in view of the high temperature viscosity control that satisfies the alkali metal oxide content of the low melting point glass frit X (M ₂ O) (weight%) and zinc oxide content X (ZnO) to the (mass%) Equation (5) Do.

1.0≤X (M ₂ O) / X (ZnO) ≤3.0 (5)

To the _{X (M 2 O) / X} (ZnO) , which is designed to range from 1.0 to 3.0 are preferred in view of the high temperature viscosity control. If it is less than 1.0, high temperature viscosity will become high too much, and if larger than 3.0, it will become too low on the contrary.

In addition, the low-melting glass is used in addition to the alkali metal oxide and lead oxide, and the stability and crystallinity of the glass by using an oxide of silicon oxide, boron oxide, aluminum oxide, alkaline earth metal (magnesium, calcium, barium, strontium, and the like). Properties, transparency, thermal expansion characteristics, and the like can be controlled. As these compositions, by setting it as the composition shown below, the low melting-point glass of the viscosity characteristic used for this invention can be produced.

Alkali metal oxides 4 to 10% by mass

Zinc oxide 3 to 10% by mass

Silicon oxide 20 to 40% by mass

Boron oxide 25 to 33 mass%

Aluminum oxide 10 to 30% by mass

Alkaline earth metal oxides 5 to 15% by mass

In addition, an alkaline earth metal refers to one or more types chosen from magnesium, calcium, barium, and strontium.

Silicon oxide content X (SiO ₂ ) (mass%), aluminum oxide content X (Al ₂ O ₃ ) (mass%) and content of boron oxide X (B ₂ O ₃ ) (mass) It is preferable that%) satisfy | fills following formula (6).

1.5 <(X (SiO ₂ ) + X (Al ₂ O ₃ )) / X (B ₂ O ₃ ) <2.0 (6)

Boron oxide is effective in order to improve the flow characteristic at the high temperature of glass, but on the contrary, it is easy to change the fluidity | liquidity or viscosity with respect to temperature. On the contrary, silicon oxide and aluminum oxide reduce the fluidity at high temperature, but have an effect of reducing the viscosity change with respect to temperature. Thus, by satisfying the above relationship, it is possible to appropriately maintain the viscosity change with respect to temperature while maintaining fluidity at high temperature.

In addition to the above, oxides selected from titanium oxide, zirconium oxide, bismuth oxide, and various metal oxides can be added, but these oxides are preferably less than 10% by mass. If 10 mass% or more is added, there exists a problem that a characteristic of glass may be impaired by discoloration and crystallization, or a cost becomes high.

As a viscosity characteristic at the high temperature of the low softening point glass powder used for this invention, it can measure using the "penetration method" which measures the measurement of the viscosity (medium viscosity range) when glass softens and sinters as mentioned above. . A measuring apparatus can be measured using a high temperature penetration type | mold viscosity meter (product number: PVM-1400) made from (Yu-O) Corporation. The viscosity can be calculated | required by measuring the load weight by a load cell using a glass sample. The actual measurement pushes a penetration indenter into a flat glass sample surface at a constant penetration speed, and measures a viscosity from the weight applied to a penetration rod by the following formula.

η = G × W / V

η: viscosity, G: device constant, W: load weight (g) to penetration rod, V: penetration velocity (mm / sec)

(Reference: 「Materials」, Vol. 15, No. 155, page 567 (1966))

As a particle diameter of the low melting glass powder used for the paste composition of this invention, it is preferable that 50% volume average particle diameter (D50) exists in the range of 1.0-4.0 micrometers. When the particle size is less than 1.0 µm, the aggregation of the particles becomes stronger, whereby the uniform dispersibility is hardly obtained, and the fluidity of the paste becomes unstable. In this case, thickness uniformity at the time of apply | coating a paste falls. Moreover, when D50 exceeds 4.0 micrometers, the surface unevenness | corrugation of a sintered compact will become large, and it becomes easy to become a cause which a pattern fractures in a later process.

The paste composition of this invention can add ceramic particles, such as high melting glass and silica, alumina, zirconia, which are not softened at 650 degreeC other than the low melting glass powder mentioned above as a filler component. A filler can be used with low melting glass in order to control plastic shrinkage rate, and to maintain the shape of the partition which is formed. However, when the ratio to the whole inorganic fine particle exceeds 50 mass%, since the sintering of low melting glass is inhibited and a problem, such as the fall of the strength of a partition, arises, it is unpreferable. Moreover, about these fillers, it is preferable that it is 0.5-4.0 micrometers in average particle diameter for the same reason as low melting glass.

Moreover, the paste composition of this invention can use various organic components according to the process for patterning. For example, when pattern-processing by the screen printing method using the mesh screen which formed the pattern opening part with high precision, celluloses, such as ethyl cellulose and nitrocellulose, are used as a binder, and terpineol etc. are used as a solvent. It can be set as a paste with few paste residues (that is, excellent plate separation property) on the screen plate at the time of printing. In the case of sand blasting, a paste prepared using cellulose, butyral resin, acrylic resin, and organic solvent is coated and dried with a slit coater, and then a film resist is attached, and the resist film is subjected to photolithography (pattern exposure / development). The pattern can be formed by using a method, and the pattern can be formed by a method of removing the resist-removed portion by sand blasting. The more preferable processing method using the paste composition of this invention is the photosensitive paste method which uses this as a photosensitive paste containing photoreactive material as the organic composition of the paste composition. The photosensitive paste can form a high-precision pattern by the photolithography method after apply | coating and drying on a board | substrate. Moreover, by using the compound which has a urethane bond in the organic component of the paste of this invention, the stress until the organic substance is calcined and distilled off can be alleviated and pattern defect can be suppressed.

When the paste composition of the present invention is a photosensitive paste containing a photoreactive material as an organic component, and high-precision pattern formation is performed, it is necessary to adjust the refractive indexes of organic and inorganic materials to suppress light scattering in order to increase light transmittance. There is. It is necessary to have the following relationship between the average refractive index n1 of the component which remains after distilling off the solvent component of boiling point 250 degrees C or less as an organic component, and the average refractive index n2 of glass powder.

-0.1 <n1-n2 <0.1

The glass component which consists of various oxides can control a characteristic in consideration of the compounding, and also the low melting glass powder which controlled the thermal characteristic, refractive index, etc. can also be used in this invention.

The paste composition of this invention can be made into the photosensitive paste which can be pattern-processed by exposing and developing by including a photoreactive material as an organic component. As a photoreactive material, reactivity can be controlled by adding a reactive monomer, a reactive oligomer, a photoinitiator, etc. Here, the reactivity in the reactive monomer and the reactive oligomer means that when the paste is irradiated with actinic light, the reactive monomer or the reactive oligomer causes a reaction such as photocrosslinking or photopolymerization to change the chemical structure.

Specifically as a photosensitive monomer, the compound which has an active carbon-carbon double bond is mentioned, A monofunctional and polyfunctional compound which has a vinyl group, acryloyl group, a methacryloyl group, and an acrylamide group is mentioned as a functional group. In particular, it is preferable to contain 10 to 80 parts by weight of the polyfunctional acrylate compound and the methacrylate compound in the organic component in order to increase the crosslinking density at the time of curing by photoreaction and to improve the pattern formability. Since various kinds of compounds have been developed as the polyfunctional acrylate compound and methacrylate, it is possible to select appropriately from the consideration of reactivity, refractive index and the like. By using a monomer or oligomer having a urethane bond in addition to the functional group reacting in the molecule as the reactive monomer or the reactive oligomer, a paste material which is less likely to be pattern-deficient can be obtained. This is because when the low melting glass powder having the high temperature viscosity characteristic of the present invention is used, it is difficult to show rapid shrinkage during the sintering process of glass during the post-heating firing. When it is used, it is caused by a mechanism in which the organic components in the initial stage of superheat firing are decomposed and distilled off, that is, the stress relaxation in the overheating process in the state in which organic matter remains, and the pattern defect is hard to occur. By having both of these characteristics, a pattern defect can be suppressed in a wide temperature range.

The paste composition of this invention can contain the copolymer polymer which has a carboxyl group as a binder. As a copolymer which has a carboxyl group, For example, carboxyl group-containing monomers, such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, or these acid anhydrides, methacrylic acid ester, acrylic acid ester, styrene, It is obtained by selecting monomers, such as an acrylonitrile, vinyl acetate, and 2-hydroxyacrylate, and copolymerizing using an initiator like azobisisobutylonitrile. As a copolymer which has a carboxyl group, the copolymer which uses acrylic acid ester or methacrylic acid ester, and acrylic acid or methacrylic acid as a copolymerization component is preferable at the point of the low thermal decomposition temperature at the time of baking.

By containing a carboxyl group, it becomes the paste excellent in the solubility to aqueous alkali solution, and the image development after pattern exposure is attained. It is preferable that the acid value of the copolymer which has a carboxyl group is 50-150 mgKOH / g. By setting the acid value to 150 mgKOH / g or less, the developing tolerance can be widened. Moreover, the solubility with respect to the developing solution of an unexposed part does not fall by setting an acid value to 50 mgKOH / g or more. Therefore, it is not necessary to thicken the developer concentration, and peeling of an exposure part can be prevented and a high-definition pattern can be obtained. Moreover, it is also preferable that the copolymer which has a carboxyl group has an ethylenically unsaturated group in a side chain. As an ethylenically unsaturated group, an acryl group, methacryl group, a vinyl group, an allyl group, etc. are mentioned.

The paste composition of the present invention may be prepared in various forms such as glass powders and organic components, organic solvents and binders (in the case of photosensitive pastes, photoreactive materials including reactive monomers, reactive oligomers, reactive polymers, photopolymerization initiators, etc. in addition to them). The components are combined so as to have a predetermined composition, and then homogeneously mixed and dispersed by three rollers or a kneader to prepare.

Although the viscosity of a paste can be suitably adjusted with addition ratios, such as an inorganic fine particle, a thickener, an organic solvent, a plasticizer, and a sedimentation inhibitor, it is preferable that the range exists in the range of 2-200 Pa.s. For example, when applying to a board | substrate by a spin coat method, the viscosity of 2-5 Pa.s is preferable. In order to apply | coat to a board | substrate by the screen printing method and to obtain film thickness 10-20 micrometers by one application | coating, the viscosity of 50-200 Pa.s is preferable. When using the blade coater method, the die coater method, etc., the viscosity of 10-50 Pa.s is preferable.

The display member can be obtained by apply | coating the paste of this invention obtained in this way on a board | substrate, forming a pattern using various methods, and baking. The paste of the present invention can be suitably used particularly for the manufacture of a plasma display member having partition walls on a substrate. As a method of forming a pattern, the screen printing method, the sand blasting method, the photolithography method, etc. can be used, for example. The photolithography method is preferable because high precision processing is possible.

Although the example which manufactures a display member using the said paste by photolithography technique is demonstrated, this invention is not limited to this.

The paste is applied to the entire surface or partially on the substrate to form a coating film. As a coating method, methods, such as a screen printing method, a bar coater, a roll coater, a die coater, and a blade coater, can be used. The coating thickness can be adjusted by selecting the number of coating times, the viscosity of the mesh of the screen, and the paste.

Here, after apply | coating a paste on a board | substrate, it exposes using an exposure apparatus. As an exposure apparatus, a proximity exposure machine etc. can be used. In addition, when exposing large area, it can expose a large area by the exposure machine of a small exposure area by performing exposure, conveying, after apply | coating paste on a board | substrate.

After exposure, image development is performed using the solubility difference with respect to the developing solution of the exposed part and unexposed part of a coating film. The development is carried out by an immersion method, a spray method, or a brush method. As a developing solution, the organic solvent which can melt | dissolve the organic component in a paste can be used. Moreover, you may add water to the said organic solvent in the range in which the solvent power is not lost. It is preferable that a developing solution has water as a main component. When the compound which has acidic groups, such as a carboxyl group, exists in paste, it can develop with aqueous alkali solution. As the aqueous alkali solution, sodium hydroxide, sodium carbonate, calcium hydroxide aqueous solution and the like can be used, but an organic alkali aqueous solution is preferred because it is easy to remove the alkali component during firing.

As the organic alkali, aqueous solutions of inorganic alkalis such as sodium carbonate, potassium carbonate, sodium hydroxide and sodium hydrogencarbonate can be used. Moreover, you may use a general amine compound. Specifically, tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, diethanolamine, etc. are mentioned. 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, the soluble portion is not removed. If the alkali concentration is too high, the pattern portion may be peeled off and the insoluble portion may be corroded. Moreover, it is preferable in process control that image development temperature at the time of image development is performed at 20-50 degreeC.

Subsequently, baking is performed in a kiln. The firing atmosphere and temperature vary depending on the type of paste or substrate, but are fired in an atmosphere such as air, nitrogen, or hydrogen. As a kiln, a batch type kiln and a belt type continuous kiln can be used.

It is preferable to bake and hold baking for 10 to 60 minutes at the temperature of 480-610 degreeC normally. By the above process, the display member in which the pattern which becomes an inorganic substance substantially is formed on a board | substrate is obtained.

Example

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to this.

(Examples 1-8, Comparative Examples 1-4)

A. Evaluation of particle size distribution of glass powder

The average particle diameter (d ₅₀ ) and the maximum particle diameter (d _max ) of glass powder were evaluated using the particle size distribution measuring apparatus ("MT3300" by Nikki Corporation). Glass powder was thrown into the sample chamber filled with water, and the measurement was performed after performing a sonication for 300 second.

B. Softening Temperature Evaluation of Glass Powder

Endothermic end temperature in the endothermic peak from the DTA curve obtained by using a differential thermal analysis device ("Differential differential differential thermal flat TG8120" manufactured by Rigaku, Ltd.) as a standard sample and heating up from room temperature to 20 ° C / min. Was extrapolated to the tangential method to obtain the softening temperature (Ts).

C. High Temperature Viscosity Evaluation of Glass

It is measured using "penetration method" using high-temperature penetration type viscometer (product number: PVM-1400) made by OPTO Corporation. The indenter was pushed on the surface of the flat glass sample at a penetration rate of 0.1 mm / min (less than 550 ° C.) and 1.0 mm / min (550 ° C. or more), and the viscosity was measured in the following manner from the weight applied to the penetration rod.

η = G × W / V

η: viscosity, G: device constant, W: load weight (g) to penetration rod, V: penetration velocity (mm / sec)

D. Fabrication of photosensitive paste and back substrate using the same

The raw material used for the paste of Examples 1-6 and Comparative Examples 1-3 is as follows.

Photosensitive monomer M-1: trimethylolpropane triacrylate

Photosensitive monomer M-2: Tetrapropylene glycol dimethacrylate

Tourist monomer Monomer M-3: In the following formula (A), R1 and R2 are hydrogen, R3 is an ethylene oxide-propylene oxide co-oligomer, R4 is an isophorone diisocyanate residue, and the molecular weight is 19,000

R1- (R4-R3) n-R4-R2 (A)

Photosensitive polymer: 0.4-glycidyl methacrylate addition reaction was carried out with respect to the carboxyl group of the copolymer which consists of methacrylic acid / methyl methacrylate / styrene = 40/40/30 (weight average molecular weight 43000, acid value 100).

Photoinitiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (IC369 by BASF Corporation).

Polymerization inhibitor: 1,6-hexanediol-bis [(3,5-di-t-butyl-4-hydroxyphenyl) propionate])

Ultraviolet light absorber solution: 0.3 mass% solution of gamma -butyrolactone of sdan IV (made in Tokyo Okagyo Kogyo Co., Ltd.)

Viscosity modifier: Flownon EC121 (manufactured by Kyoeisha Chemical Co., Ltd.)

Solvent: γ-butyrolactone

Glass powder: The glass powders 1-6 shown in Table 1 were used.

Using the said material, the photosensitive paste of Examples 1-6 and Comparative Examples 1-3 was produced with the following method.

4 mass% of photosensitive monomer M-1, 6 mass% of photosensitive monomer M-2, 24 mass% of photosensitive polymers, 6 mass% of photoinitiators, 0.2 mass% of polymerization inhibitors, 12.8 mass% of ultraviolet absorber solutions, and 38 mass% of solvents It melt | dissolved by heating at 80 degreeC. 9 mass% of viscosity modifiers were added after cooling, and the organic solution 1 was produced. In addition, 6 mass% of photosensitive monomers M-3 were added instead of the photosensitive monomer M-2 in the said organic solution 1, and the organic solution 2 was produced.

Subsequently, after adding the glass powder shown in Table 2 to 60 mass% of the produced organic solution 1 or the organic solution 2, it knead | mixed with three roller kneaders and produced the paste. In addition, using the produced paste, a back substrate for plasma display was produced by the following method.

A stripe-shaped address silver electrode (line width 50 μm, thickness 3 μm, pitch 300 μm) was formed on a diagonal 42 inch glass substrate, and a dielectric layer having a thickness of 15 μm was formed thereon, and then the paste was dried with a thickness of 160 μm. It applied and dried so that it might become.

Next, the photomask (stripe-shaped pattern, 50 micrometers of line width, and 300 micrometers of pattern pitch) aimed at formation of the partition pattern for plasma displays was set and exposed in parallel to the address electrode. It developed in 0.5% ethanolamine aqueous solution after exposure, and baked at 595 degreeC for 15 minutes. A display member having a stripe-shaped partition wall having a pitch of 300 µm, a line width of 50 µm, and a height of 120 µm was obtained.

E. Sand blast paste and back substrate using the same

The pastes of Examples 7 and 8 and Comparative Example 4 were prepared in the following order. The organic solution 3 which melt | dissolved 5 mass% of dibutyl phthalates as a 3 mass% ethylcellulose resin and a plasticizer was prepared in the solvent which mixed terpineol and diethylene glycol monobutyl ether acetate 1: 1. After adding the glass powder shown in Table 2 to 60 mass% of said solutions, it knead | mixed with three roller kneaders, and produced the paste.

A stripe-shaped address silver electrode (line width 50 µm, thickness 3 µm, pitch 250 µm) was formed on a diagonal 42-inch glass substrate, and a dielectric layer having a thickness of 15 µm was formed thereon, and then the paste was dried to 140 µm thick. It applied and dried so that it might become.

Next, the negative type dry film resist (NCP225, 25 micrometers made by Nippon Kosei Kagaku Kogyo Co., Ltd.) which has a protective film on the paste layer was laminated with the 100 degreeC heat roll.

A pattern mask of a line and space having a pitch of 300 µm and an opening width of 50 µm was positioned on the resist layer, and was irradiated with ultraviolet radiation (364 nm, intensity of 20 mW / cm 2, irradiation amount of 120 mJ / cm 2), and then exposed to a photoresist layer. The protective film was peeled off and spray-developed using a 1 mass% aqueous solution of sodium carbonate at a liquid temperature of 30 ° C. The resist pattern according to the line pattern mask was obtained.

Subsequently, sand blasting was performed using X hyperblast apparatus HCH-3X7BBART-411M (made by Fuji Seisakusho Co., Ltd.) using this resist pattern as a mask. Furthermore, it baked at 595 degreeC for 15 minutes. A display member having a stripe-shaped partition wall having a pitch of 300 µm, a line width of 50 µm, and a height of 120 µm was obtained.

F. Evaluation of Pattern Defects

Pattern defects, such as a disconnection, were observed after baking. Table 2 shows the results of evaluation by counting the number of pattern defects.

In addition, evaluation of disconnection starting size was performed as the evaluation of the ease of generation of a pattern defect by the following method. In the exposure using the photomask, a mask in which 40 pattern defects each having a size of 5 to 40 µm is formed on the photomask (a light-emitting slit having a predetermined width is formed at each opening) is used, and at least 50% of the mask defects are used. The pattern defect size which is disconnected (produced 40 pattern defects of the same size in a mask and disconnected at 20 or more places among them) was made into disconnection start size. This evaluation becomes evaluation which shows how much a pattern defect is easy to occur when a mask is damaged or a foreign material adheres in a process, and it is so preferable that it is large.

Table 2 shows the evaluation results of the photosensitive pastes obtained in Examples 1 to 8 and Comparative Examples 1 to 4.

(Industrial applicability)

This invention can be usefully used as a paste for forming the partition with few residual organic components. Moreover, the partition which has few residual organic components is formed, and it is excellent in display characteristics, such as a brightness | luminance and a color purity, and can be useful as a flat panel display with high panel reliability.

Claims (7)

As a paste composition containing a glass powder and an organic component, the low-melting-point glass powder in which viscosity (eta) 1 (dPa * s) at 570 degreeC and viscosity (eta2) (dPa * s) at 590 degreeC satisfy | fills following formula (1) 40 mass% or more with respect to all the glass powder, The paste composition characterized by the above-mentioned.
0.5 <logη1-logη2 <0.9 (1) A paste composition comprising a glass powder and an organic component, wherein the glass powder has a low melting point glass at which viscosity η 1 (dPa · s) at 570 ° C. and viscosity η 2 (dPa · s) at 590 ° C. satisfy the following formula (2): A paste composition comprising 40% by mass or more of the powder relative to the total glass powder.
1.05 <logη1 / logη2 <1.11 (2) 3. The method according to claim 1 or 2,
The said (eta) (dPa * s) and (eta2) (dPa * s) satisfy | fill following formula (3) and formula (4), The paste composition characterized by the above-mentioned.
8.5 <logη1 <9.0 (3)
7.8 <logη2 <8.5 (4) The method according to any one of claims 1 to 3,
The softening temperature of the said low melting glass powder is 560-610 degreeC, The paste composition characterized by the above-mentioned. The method according to any one of claims 1 to 4,
The low-melting glass powder in satisfying the alkali metal oxide content X (M ₂ O) (weight%) and zinc oxide content X (ZnO) to the (mass%) Equation (5), and oxidation of the low melting point glass frit Silicon content X (SiO ₂ ) (mass%), aluminum oxide content X (Al ₂ O ₃ ) (mass%) and content of boron oxide X (B ₂ O ₃ ) (mass%) satisfy the following formula (6): In addition, the content X (M ₂ O) of the alkali metal oxide in the low melting point glass powder is in the range of 4 to 10% by mass, and the content X (ZnO) of zinc oxide is in the range of 3 to 10% by mass. Paste composition, characterized in that.
1.0≤X (M ₂ O) / X (ZnO) ≤3.0 (5)
1.5 <(X (SiO ₂ ) + X (Al ₂ O ₃ )) / X (B ₂ O ₃ ) <2.0 (6) 6. The method according to any one of claims 1 to 5,
A paste composition comprising a photoreactive material as an organic component. A partition wall is formed using the paste composition as described in any one of Claims 1-6, The manufacturing method of the plasma display characterized by the above-mentioned.