JPH10269934A - Manufacture of plasma display panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To facilitate bulkhead forming with thin line width and provide a high-precision plasma display by setting a ratio of a line width L1 of a photo mask within a specific range with respect to a line width L2 of a bulkhead pattern before burning when the bulkhead of a plasma display panel is manufactured. SOLUTION: After applying a photosensitive glass paste containing a light reactive organic component and a glass powder onto a glass substrate, this display is manufactured through each of exposure, developing, and burning processes using a photo mask. If a line width of a bulkhead is thinned for high precision, thickening of patterns due to light scattering cannot be ignored. To solve this problem, a line width L1 of the photo mask meets an equation: L2/L1=1.1 to 5 with respect to a line width L2 of bulkhead patterns after developing and before burning, thereby making it possible to manufacture the bulkhead for a plasma display panel of its desired line width. Hereby L2 denotes a half value width with respect to a height of the bulkhead.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a partition of a plasma display and a plasma addressed liquid crystal display.

[0002]

2. Description of the Related Art Plasma display panels (PDPs)
Since they can display at a higher speed than a liquid crystal panel and can be easily made larger, they have permeated OA equipment and public information display devices. Further, progress in the field of high-definition television is highly expected.

With the expansion of such applications, attention has been paid to color PDPs having delicate and many display cells. The PDP generates plasma discharge between opposing anode and cathode electrodes in a discharge space provided between the front glass substrate and the rear glass substrate, and emits ultraviolet light generated from a gas sealed in the discharge space. The display is performed by hitting a phosphor provided in the discharge space. In this case, a partition (also referred to as a barrier or a rib) is provided to suppress the spread of the discharge to a certain area and perform display in a specified cell, and to secure a uniform discharge space. The shape of the partition wall is approximately 30 to 8 in width.
0 μm and height of 100 to 200 μm, usually, an insulating paste made of glass is printed and dried on the front glass substrate and the rear glass substrate by a screen printing method, and the printing and drying process is repeated 10 to 20 times to obtain a predetermined value. After height
It is formed by firing. However, in the normal screen printing method, especially when the panel size is increased,
It is difficult to align the discharge electrode formed on the front transparent flat plate in advance with the printing place of the insulating glass paste,
There is a problem that it is difficult to obtain positional accuracy. In addition, by performing the superposition printing of the glass paste 10 to 20 times, the ribs and the edge of the side wall of the partition wall and the skirt are disturbed, and the accuracy of the height cannot be obtained, so that the display quality is deteriorated. There are problems of poor workability and low yield. In particular, the pattern width is 50 μm and the pitch is 100 μm
Below this, there is a problem that the bottom of the partition wall is easily spread due to the thixotropic property of the paste, and it is difficult to form a sharp and residue-free partition wall.

[0004] With the increase in the area and resolution of PDPs, such a screen printing method makes it difficult and more costly to manufacture partition walls having a high aspect ratio and high definition. Is coming.

As a method for improving these problems, Japanese Patent Application Laid-Open Nos. 1-2296534, 2-165538, 5-342929, and 6-29 have been proposed.
No. 5676 proposes a method of forming a partition by a photolithography technique using a photosensitive paste. However, according to these methods, there are problems that a dense partition wall cannot be obtained after firing and that the sensitivity and resolution of the photosensitive insulating paste are low because the glass content of the photosensitive insulating paste is small. For this purpose, screen printing
It was necessary to obtain a partition wall having a high aspect ratio by repeatedly performing the exposure and development steps. However, if printing, exposure, and development are repeatedly performed, there is a problem of alignment, and there is a limit to cost reduction.

Japanese Patent Application Laid-Open No. 8-50811 proposes a method in which a partition is formed by one exposure using a photosensitive glass paste method. However, even with this method, when a pattern with a reduced line width is formed, the pattern accuracy is not sufficient.

[0007]

The present invention relates to a method for manufacturing a partition for a plasma display. An object of the present invention is to provide a high-definition plasma display by facilitating formation of a partition having a small line width. Another object of the present invention is to provide a high-brightness, high-definition plasma display having excellent discharge characteristics.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to apply a photosensitive glass paste containing a photoreactive organic component and a glass powder as essential components on a glass substrate, and then expose, develop, and bake using a photomask. Wherein the line width L1 of the photomask satisfies the following expression with respect to the line width L2 of the partition wall pattern before firing when the partition wall of the plasma display panel is manufactured through the above steps. Is achieved by

L2 / L1 = 1.1 to 5 Another object of the present invention is to provide a plasma display characterized in that the line width L1 of the photomask satisfies the following expression with respect to the line width L3 of the partition after firing. Is achieved.

L3 / L1 = 0.8-3.5

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the method of manufacturing a partition for a plasma display of the present invention, a photosensitive glass paste containing a photoreactive organic component and a glass powder as essential components is applied on a glass substrate, and then exposed using a photomask. It is manufactured through development and firing processes.

Normally, when patterning is performed by photolithography using a photosensitive material, the line width L1 of the mask is designed to match the line width of the desired pattern L2. The state where the exposure amount is optimized and the pattern shape after development is rectangular is expressed by the following equation. L2 / L1 = 1 However, in the case where the partition is to be formed by the photosensitive glass paste, the line width of the partition pattern becomes thicker than the mask width, and there has been a problem that it is difficult to form a desired pattern. For the purpose of high definition, high aperture ratio, and high brightness of the plasma display panel, as the line width of the desired partition wall becomes thinner, the thickness of the pattern due to light scattering cannot be ignored,
It becomes difficult to form a partition pattern having a desired line width.
To avoid this, it is necessary to adjust the exposure amount. For example, when using a photo-insolubilizing resin as a photo-reactive organic component, it is necessary to reduce the exposure amount, but then the photo-curing reaction does not proceed sufficiently to the lower part of the pattern,
At the time of development, a problem of peeling occurs.

The present invention solves this problem by controlling the ratio between the line width L1 of the exposure mask and the line width L2 of a desired partition pattern to a specific ratio. Here, when the line width L1 of the photomask satisfies the following expression with respect to the line width L2 of the partition pattern after development and before firing, it becomes possible to manufacture a partition for a plasma display having a desired line width. L2 / L1 = 1.1 to 5 Here, L2 indicates a half width with respect to the height of the partition wall.

When L2 / L1 is less than 1.1, the line width of the mask becomes too large with respect to the line width of the barrier rib pattern after development, so that the line width tends to be larger than a desired line width. If the exposure amount is reduced to avoid this, for example, when obtaining a partition height of 130 to 180 μm before baking, the photocuring reaction does not sufficiently proceed to the lower part of the pattern, which causes a problem of peeling during development, which is not preferable. Also, in order to avoid peeling during development, it is conceivable to reduce the line width of the partition pattern by lengthening the development time instead of lowering the exposure amount. However, according to this method, the partition pattern of the insolubilized portion may be reduced. Are swelled by the developer and meander, which makes it difficult to form a pattern.

When L2 / L1 exceeds 5, the line width of the mask becomes too small with respect to the line width of the partition pattern, and it is necessary to increase the exposure in order to obtain a desired line width.
For example, when a desired line width is obtained at a height before baking of 130 to 180 μm, curing progresses to the bottom of the pattern and the effect of light scattering increases, the cross section becomes an irregular trapezoidal shape. Are connected to form a residual film. For this reason, a sufficient discharge space cannot be secured, and the luminance of the panel decreases, which is not preferable. Further, when the partition wall pitch is in a narrow range of 100 to 160 μm, light is scattered in portions other than the light-shielding portion of the mask, a curing reaction proceeds, and a film remaining at the time of development is generated, and a sufficient pattern cannot be obtained. More preferably, L2 / L1 = 1.1-3
Is superior in terms of securing the aperture ratio, avoiding falling and meandering.

The partition pattern obtained by the development is thereafter cured by firing. The firing temperature depends on the softening point (Ts) of the glass powder contained in the paste.
s + 5 to 70 ° C. is preferable. Raise the temperature with a predetermined program, remove the binder from the organic components in the paste,
Further, the glass is melted and sintered.

In general, the height and line width of the partition pattern after firing are smaller than those after development. Here, it is preferable that the line width L3 of the partition after firing satisfies the following expression. L3 / L2 = 0.6 to 0.85 When L3 / L2 is less than 0.6, the upper end of the partition wall is rounded,
The contact area with the opposing substrate at the time of panel assembly becomes small, and it is difficult to obtain sufficient insulation characteristics at the time of discharge. Under the firing conditions where L3 / L2 exceeds 0.85, sintering becomes insufficient, the porosity increases, and it is difficult to obtain sufficient hardness, adhesion, and insulation.

Therefore, it is preferable that the line width L3 of the partition after firing and the line width L1 of the photomask satisfy the following expression. L3 / L1 = 0.8-3.5 When the ratio is in this range, it is possible to obtain a partition wall without peeling, falling, and meandering.

Assuming that the pitch is P, the line width is L, and the height is H, the shape of each part of the partition wall pattern of the present invention has the following relationship in terms of panel luminance and discharge life. Is preferred.

When P = 100 to 140 μm, L = 15 to 50 μm, H = 100 to 170 μm. When P = 140 to 160 μm, L = 20 to 60 μm, H = 150 to 220 μm. Then, peeling and falling during pattern formation, and disconnection and peeling after firing are likely to occur. Above the upper limit, a decrease in luminance occurs due to a decrease in the aperture ratio of the partition wall obtained after firing,
Not preferred.

When the height is smaller than the above lower limit,
Since the discharge space of the partition wall obtained after baking becomes narrow, the plasma region becomes close to the phosphor, and the phosphor is sputtered, which is not preferable in terms of life. If it is larger than the above upper limit, the ultraviolet light generated by the discharge is absorbed before reaching the phosphor, which lowers the luminance, which is not preferable.

The porosity of the partition wall in the present invention is 3 because of its excellent adhesion to the substrate for preventing the partition wall from falling down.
% Is preferable. The porosity (P) is defined as P = (dth−dex) / dth × 100, where dth is the theoretical density of the partition wall material and dex is the measured density of the partition wall. The theoretical density is calculated from the component ratio of the partition and the specific gravity of each component. The measurement of the measured density is preferably performed using the ordinary Archimedes method.

If the porosity is more than 3%, not only the adhesion is deteriorated, but also the strength is insufficient and the discharge characteristics are deteriorated, such as a decrease in luminance due to gas and moisture discharged from the pores during discharge. Considering the discharge characteristics such as the discharge life and luminance stability of the panel, it is more preferably 0.5% or less.

The method for producing the partition wall of the present invention is not particularly limited, but it is preferable to produce the partition wall by a photosensitive glass paste method which has few steps and can form a fine pattern.

In the photosensitive glass paste method, a photomask pattern is baked by exposure using a photosensitive glass paste mainly composed of an inorganic component composed of glass powder and an organic component having photosensitivity, and a partition pattern is formed by development. And then firing to obtain partition walls.

When used for a partition of a plasma display or a plasma addressed liquid crystal display, a pattern is formed on a glass substrate having a low glass transition point and a low thermal softening point.
It is preferable to use a glass material having a temperature of 470 ° C and a thermal softening temperature of 470 to 580 ° C. If the glass transition point is 500 ° C and the thermal softening point is higher than 580 ° C, it must be fired at a high temperature,
During firing, the substrate is distorted. The glass transition point is 4
A material having a temperature of 30 ° C. and a thermal softening point lower than 470 ° C. is not preferable because the partition walls are distorted when the phosphor is applied and fired in a subsequent step, causing peeling and disconnection.

Since the general high strain point glass used for the substrate glass has a linear expansion coefficient of 80 to 90 × 10 −7, the linear thermal expansion coefficient is 50 to prevent the substrate from warping. ~ 90 × 10 -7, moreover, 60 ~ 90 × 1
It is preferable to use a glass material of 0-7.

The amount of the glass powder used in the photosensitive glass paste method is 65 to 8 with respect to the sum of the glass powder and the organic component.
Preferably it is 5% by weight.

If the content is less than 65% by weight, the shrinkage ratio during firing becomes large, which causes disconnection and peeling of the partition walls.
Not preferred. In addition, the pattern tends to be thick and a residual film is likely to be generated during development. If it is more than 85% by weight, the pattern formability deteriorates due to the small amount of the photosensitive component.

With respect to the composition of the partition wall material, silicon oxide is preferably incorporated in the glass in the range of 3 to 60% by weight, and if less than 3% by weight, the denseness, strength and stability of the glass layer are reduced. In addition, the coefficient of thermal expansion deviates from a desired value, and a mismatch with a glass substrate is likely to occur. Further, when the content is set to 60% by weight or less, there is an advantage that the heat softening point is lowered and baking on a glass substrate becomes possible.

Boron oxide is contained in the glass in an amount of 5 to 50% by weight.
The electrical, mechanical and thermal properties such as electrical insulation, strength, coefficient of thermal expansion, and denseness of the insulating layer can be improved by blending in the range. If it exceeds 50% by weight, the stability of the glass will decrease.

It can also be obtained by using glass fine particles containing at least one of lithium oxide, sodium oxide and potassium oxide in an amount of 2 to 20% by weight.
The amount of the oxide of an alkali metal such as lithium, sodium, and potassium is 20% by weight or less, preferably,
By setting the content to 15% by weight or less, the stability of the paste can be improved.

As the glass composition containing lithium oxide,
In terms of oxide, lithium oxide 2 to 10 parts by weight Silicon oxide 10 to 50 parts by weight Boron oxide 20 to 40 parts by weight Barium oxide 2 to 15 parts by weight Aluminum oxide 6 to 25 parts by weight 50% or more by weight It is preferred to contain.

In the above composition, sodium oxide or potassium oxide may be used instead of lithium oxide.
Lithium oxide is preferred from the viewpoint of paste stability.

By using glass particles containing at least one of bismuth oxide, lead oxide and zinc oxide in a glass in an amount of 5 to 50% by weight, a photosensitive glass paste having a temperature characteristic capable of patterning on a glass substrate can be obtained. Obtainable. If it exceeds 50% by weight, the heat-resistant temperature of the glass becomes too low, and it is difficult to bake the glass on a glass substrate. In particular, using glass containing 5 to 50% by weight of bismuth oxide has advantages such as a long pot life of the paste.

The glass composition containing bismuth oxide includes:
Bismuth oxide 10 to 40 parts by weight in terms of oxides Silicon oxide 3 to 50 parts by weight Boron oxide 10 to 40 parts by weight Barium oxide 8 to 20 parts by weight Aluminum oxide 10 to 30 parts by weight 50% or more by weight It is preferred to contain.

In addition, a glass containing both a metal oxide such as lead oxide, bismuth oxide and zinc oxide and an alkali metal oxide such as lithium oxide, sodium oxide and potassium oxide enables a thermal treatment at a lower alkali content. Control of softening temperature and linear thermal expansion coefficient becomes easy.

Further, by adding aluminum oxide, barium oxide, calcium oxide, magnesium oxide, zinc oxide, zirconium oxide, and the like, particularly aluminum oxide, barium oxide, and zinc oxide to the glass fine particles, the advanced properties and workability are improved. However, from the viewpoint of controlling the thermal softening point, the coefficient of thermal expansion, and the refractive index, the content is preferably 40% by weight or less, more preferably 25% by weight or less. Further, glass generally used as an insulator has a refractive index of about 1.5 to 1.9, but when the photosensitive glass paste method is used, the average refractive index of the organic component is lower than that of the glass powder. When the ratio is significantly different from the ratio, reflection and scattering at the interface between the glass powder and the photosensitive organic component become large, and a fine pattern cannot be obtained. Since the refractive index of a general organic component is 1.45 to 1.7, the average refractive index of the glass powder is set to 1.5 to 1.65 in order to match the refractive indexes of the glass powder and the organic component. Is preferred.

2 to 10% by weight of alkali metal oxides such as sodium oxide, lithium oxide and potassium oxide in total
By using the glass contained, not only the control of the thermal softening temperature and the coefficient of thermal expansion becomes easy, but also the average refractive index of the glass can be lowered, so that the difference in the refractive index from the organic substance can be easily reduced. become. If it is less than 2%, it becomes difficult to control the thermal softening temperature. When it is more than 10%, the brightness is reduced due to evaporation of the alkali metal oxide during discharge. Further, the addition amount of the oxide of the alkali metal is set at 10 to improve the stability of the paste.
It is preferably less than 8% by weight, more preferably less than 8% by weight.

In particular, the use of lithium oxide among the alkali metals makes it possible to relatively increase the stability of the paste. In the case of using potassium oxide,
Among the alkali metal oxides, the addition of lithium oxide and potassium oxide is effective because there is an advantage that the refractive index can be controlled by adding a relatively small amount.

As a result, it has a heat softening temperature that can be baked on a glass substrate, can have an average refractive index of 1.5 to 1.65, and can easily reduce the difference in refractive index from the organic component. become.

Glass containing bismuth oxide is preferred from the viewpoint of improving the heat softening temperature and water resistance.
Glass containing 0% by weight or more often has a refractive index of 1.6 or more. So sodium oxide, lithium oxide,
By using an oxide of an alkali metal such as potassium oxide and lead oxide in combination, it becomes easy to control the thermal softening temperature, thermal expansion coefficient, water resistance and refractive index.

The measurement of the refractive index of the glass material in the present invention is accurate at the wavelength of the light exposed by the photosensitive glass paste method in order to confirm the effect. In particular, 35
It is preferable to measure with light having a wavelength in the range of 0 to 650 nm. Further, i-line (365 nm) or g-line (4
(36 nm) is preferred.

The partition walls of the present invention may be colored black because they are excellent in increasing the contrast. By adding various metal oxides, the partition walls after firing can be colored. For example, by containing 1 to 10% by weight of a black metal oxide in the photosensitive paste,
A black pattern can be formed.

As the black metal oxide used at this time,
By including at least one, and preferably three or more of the oxides of Cr, Fe, Co, Mn, and Cu, blackening becomes possible. In particular, a black pattern can be formed by containing 0.5% by weight or more of each of the oxides of Fe and Mn.

Furthermore, in addition to black, a pattern of each color can be formed by using a paste to which an inorganic pigment that develops red, blue, green or the like is added. These coloring patterns can be suitably used for a color filter of a plasma display and the like.

The dielectric constant of the partition wall glass member is preferably 4 to 10 at a frequency of 1 MHz and a temperature of 20 ° C. from the viewpoint of excellent power consumption and discharge life of the panel. In order to reduce the value to 4 or less, a large amount of silicon oxide having a dielectric constant of about 3.8 must be contained, and the glass transition point is increased and the firing temperature is increased. If it is 10 or more, power loss due to an increase in the amount of charge occurs, which causes an increase in power consumption, which is not preferable.

The specific gravity of the partition wall of the present invention is preferably from 2 to 3.3. In order to reduce the content to 2 or less, the glass material must contain a large amount of an oxide of an alkali metal such as sodium oxide or potassium oxide, which is unfavorable because it evaporates during the discharge and lowers the discharge characteristics. . When it is 3.3 or more, the display becomes heavy when the screen is enlarged, or the substrate is distorted by its own weight, which is not preferable.

The partition wall material of the present invention has a glass softening point of 650.
A filler having a temperature of ８850 ° C. may be contained in an amount of 10５０50% by weight. Thereby, in the photosensitive glass paste method, the shrinkage ratio during firing after pattern formation is reduced, and pattern formation is facilitated. As the filler, high melting point glass or ceramics having a thermal softening temperature of 600 ° C. or higher can be used.

As the high melting point glass powder, a glass powder containing 15% by weight or more of silicon oxide and aluminum oxide is preferable, and the total content of these should be 50% by weight or more in the glass powder. It is effective to have. As an example, it is preferable to use a glass powder containing the following composition.

Silicon oxide: 15 to 50% by weight Boron oxide: 5 to 20% by weight Aluminum oxide: 15 to 50% by weight Barium oxide: 2 to 10% by weight Organic components are photosensitive monomers, photosensitive oligomers, and photosensitive polymers. And a binder, a photopolymerization initiator, an ultraviolet absorber, a sensitizer, a sensitization aid, a polymerization inhibitor, a plasticizer, and a thickener, if necessary. Agents, organic solvents, antioxidants, dispersants,
Additive components such as organic or inorganic suspending agents may be added.

The photosensitive component includes a photo-insolubilizing type and a photo-solubilizing type. The photo-insolubilizing type includes: (A) a functional monomer having at least one unsaturated group in the molecule. (B) those containing photosensitive compounds such as aromatic diazo compounds, aromatic azide compounds, and organic halogen compounds. (C) So-called diazo resins such as condensates of diazo amines and formaldehyde. And others.

Examples of the photo-soluble type include (D) a complex of a diazo compound with an inorganic salt or an organic acid, and a compound containing a quinone diazo compound. (E) a quinone diazo compound combined with an appropriate polymer binder. For example, phenol, naphthoquinone-1,2-diazide-5-sulfonic acid ester of a novolak resin, and the like.

As the photosensitive component used in the present invention, all of the above can be used. As the photosensitive component which can be easily used as a photosensitive paste by being mixed with inorganic fine particles, (A) is preferred.

The photosensitive monomer is a compound containing a carbon-carbon unsaturated bond, and specific examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, and sec-butyl. Acrylate, sec-
Butyl acrylate, iso-butyl acrylate, te
rt-butyl acrylate, n-pentyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxytriethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate Heptadecafluorodecyl acrylate, 2-hydroxyethyl acrylate, isobonyl acrylate, 2-hydroxypropyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-
Methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, allylated cyclohexyl diacrylate, 1,4-butanediol diacrylate, 1,3-butylene Glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, ditrimethylolpropane tetraacrylate, glycerol diacrylate, methoxide Shi of cyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, triglycerol diacrylate,
Trimethylolpropane triacrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, benzyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, bisphenol A diacrylate, diacrylate of bisphenol A-ethylene oxide adduct,
Diacrylates of bisphenol A-propylene oxide adducts, acrylates such as thiophenol acrylate and benzyl mercaptan acrylate, and monomers in which 1 to 5 hydrogen atoms of these aromatic rings have been substituted with chlorine or bromine atoms, or Styrene, p-
Methylstyrene, o-methylstyrene, m-methylstyrene, chlorinated styrene, brominated styrene, α-methylstyrene, chlorinated α-methylstyrene, brominated α-methylstyrene, chloromethylstyrene, hydroxymethylstyrene, carboxy Methyl styrene, vinyl naphthalene, vinyl anthracene, vinyl carbazole, and those obtained by changing some or all of the acrylate in the molecule of the above compound to methacrylate, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone, etc. Is mentioned. In the present invention, one or more of these can be used.

In addition to these, the developability after exposure can be improved by adding an unsaturated acid such as an unsaturated carboxylic acid. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof.

The content of these monomers is preferably 5 to 30% by weight based on the sum of the glass powder and the photosensitive component.
Outside of this range, the pattern formability deteriorates and the hardness becomes insufficient after curing.

As the binder, polyvinyl alcohol, polyvinyl butyral, methacrylate polymer, acrylate polymer, acrylate ester
Examples include methacrylate copolymers, α-methylstyrene polymers, and butyl methacrylate resins.

An oligomer or polymer obtained by polymerizing at least one of the compounds having a carbon-carbon double bond described above can be used. During the polymerization, the copolymer may be copolymerized with another photosensitive monomer so that the content of the photoreactive monomer is 10% by weight or more, more preferably 35% by weight or more.

As a monomer to be copolymerized, the developability after exposure can be improved by copolymerizing an unsaturated acid such as an unsaturated carboxylic acid. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof.

The polymer or oligomer having an acidic group such as a carboxyl group in the side chain thus obtained has an acid value (AV) of preferably from 50 to 180, more preferably from 70 to 140. When the acid value is less than 50, the allowable development width becomes narrow. On the other hand, if the acid value exceeds 180, the solubility of the unexposed portion in the developing solution decreases, so that if the developing solution concentration is increased, peeling occurs up to the exposed portion, making it difficult to obtain a high-definition pattern.

By adding a photoreactive group to a side chain or a molecular end of the polymer or oligomer described above, it can be used as a photosensitive polymer or a photosensitive oligomer having photosensitivity. Preferred photoreactive groups are those having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acryl group, and a methacryl group.

The method of adding such a side chain to an oligomer or a polymer is based on a method in which an ethylenically unsaturated compound having a glycidyl group or an isocyanate group or an acrylic acid is added to the mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. There is a method in which chloride, methacrylic chloride or allyl chloride is added to make an addition reaction.

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 ether crotonic acid and glycidyl ether isocrotonic acid. .

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

The ethylenically unsaturated compound having a glycidyl group or an isocyanate group, acrylic acid chloride, methacrylic acid chloride or allyl chloride is used in an amount of 0.05 to 0.05 to the mercapto group, amino group, hydroxyl group and carboxyl group in the polymer. It is preferable to add one molar equivalent.

The amount of the polymer component comprising the photosensitive polymer, the photosensitive oligomer and the binder in the photosensitive glass paste is excellent in terms of pattern formability and shrinkage after firing. It is preferably 5 to 30% by weight based on the sum of the components. Outside this range, it is not preferable because pattern formation is impossible or the pattern becomes thick.

As specific examples of the photopolymerization initiator,
Benzophenone, methyl o-benzoylbenzoate, 4,
4-bis (dimethylamine) benzophenone, 4,4-
Bis (diethylamino) benzophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenylketone, dibenzylketone, fluorenone, 2,
2-diethoxyacetophenone, 2,2-dimethoxy-
2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, Benzyl dimethyl ketanol, benzyl methoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone,
2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methyleneanthrone,
4-azidobenzalacetophenone, 2,6-bis (p
-Azidobenzylidene) cyclohexanone, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadione-2- (o
-Methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o
-Ethoxycarbonyl) oxime, 1-phenyl-3-
Ethoxy-propanetrione-2- (o-benzoyl)
Oxime, Michler's ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, naphthalenesulfonyl chloride, quinoline sulfonyl chloride, N-phenylthioacridone, 4,4
-Azobisisobutyronitrile, diphenyl disulfide, benzothiazole disulfide, triphenylphorphine, camphorquinone, carbon tetrabromide, tribromophenylsulfone, benzoin peroxide and eosin,
Examples include a combination of a photoreducing dye such as methylene blue and a reducing agent such as ascorbic acid and triethanolamine. In the present invention, one or more of these can be used.

The photopolymerization initiator is used in an amount of 0.
In the range of 0.5 to 20% by weight, more preferably
0.1 to 15% by weight. If the amount of the polymerization initiator is too small, the photosensitivity becomes poor, and if the amount of the photopolymerization initiator is too large, the residual ratio of the exposed portion may be too small.

It is also effective to add an ultraviolet absorber. By adding a compound having a high ultraviolet absorption effect, a high aspect ratio, high definition, and high resolution can be obtained. UV absorbers composed of organic dyes, especially 35
Organic dyes having a high UV absorption coefficient in the wavelength range of 0 to 450 nm are preferably used. Specifically, azo dyes, aminoketone dyes, xanthene dyes, quinoline dyes, aminoketone dyes, anthraquinones, benzophenones, diphenylcyanoacrylates, triazines, p-aminobenzoic acid dyes and the like can be used. . Even when the organic dye is added as a light absorbing agent, it is preferable because deterioration of the insulating film characteristics due to the light absorbing agent can be reduced without remaining in the insulating film after firing. Among these, azo dyes and benzophenone dyes are preferred.

The amount of the organic dye added is preferably 0.05 to 1 part by weight based on the glass powder. When the content is less than 0.05% by weight, the effect of adding the ultraviolet absorbent is reduced, and when it exceeds 1% by weight, the properties of the insulating film after firing are deteriorated, which is not preferable. More preferably, it is 0.1 to 0.18% by weight.

One example of the method of adding the ultraviolet light absorber composed of an organic dye is as follows. In addition to the method of preparing a solution in which an organic dye is dissolved in an organic solvent in advance and kneading the solution at the time of preparing the paste, the method of adding glass After mixing the fine particles, a method of drying the fine particles can be used. By this method, so-called capsule-like fine particles in which the surface of each glass fine particle is coated with an organic film can be produced.

In the present invention, P contained in inorganic fine particles
Metals and oxides such as b, Fe, Cd, Mn, Co, and Mg may react with the photosensitive components contained in the paste, causing the paste to gel in a short time, making application impossible. In order to prevent such a reaction, it is preferable to add a stabilizer to prevent gelation. As the stabilizer used, a triazole compound is preferably used. As the triazole compound, a benzotriazole derivative is preferably used. Among them, benzotriazole works particularly effectively. As an example of the surface treatment of glass fine particles with benzotriazole used in the present invention, a predetermined amount of benzotriazole with respect to inorganic fine particles methyl acetate, ethyl acetate, ethyl alcohol,
After dissolving in an organic solvent such as methyl alcohol, 1-2 parts of the solution are dissolved in the solution so that these fine particles can be sufficiently immersed.
Soak for 4 hours. After immersion, preferably, the particles are naturally dried at 20 to 30 ° C., and the solvent is evaporated to produce triazole-treated fine particles. The ratio of the stabilizer used (stabilizer / inorganic fine particles) is preferably 0.05 to 5% by weight.

The sensitizer is added to improve the sensitivity. Specific examples of the sensitizer include 2,4-diethylthioxanthone, 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-
Dimethylaminobenzal) acetone, 1,3-carbonyl-bis (4-diethylaminobenzal) acetone,
3,3-carbonyl-bis (7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N
-Phenylethanolamine, N-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, 1-phenyl-5-ethoxycarbonylthiotetrazole and the like. Can be In the present invention, one or more of these can be used. Some sensitizers can also be used as photopolymerization initiators. When a sensitizer is added to the photosensitive paste of the present invention, the amount is usually 0.05 to 10% by weight, more preferably 0.1 to 10% by weight, based on the photosensitive component. 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 too small.

The polymerization inhibitor is added to improve the thermal stability during storage. Specific examples of the polymerization inhibitor include hydroquinone, monoesterified hydroquinone,
N-nitrosodiphenylamine, phenothiazine, p-
t-butylcatechol, N-phenylnaphthylamine,
2,6-di-t-butyl-p-methylphenol, chloranil, pyrogallol and the like. When adding a polymerization inhibitor, the amount added, in the photosensitive paste,
Usually, it is 0.001 to 1% by weight.

Specific examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, polyethylene glycol, glycerin and the like.

The antioxidant is added to prevent oxidation of the acrylic copolymer during storage. Specific examples of antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, and 2,6-di-t.
-4-ethylphenol, 2,2-methylene-bis-
(4-methyl-6-t-butylphenol), 2,2-
Methylene-bis- (4-ethyl-6-t-butylphenol), 4,4-bis- (3-methyl-6-t-butylphenol), 1,1,3-tris- (2-methyl-6
-T-butylphenol), 1,1,3-tris- (2
-Methyl-4-hydroxy-t-butylphenyl) butane, bis [3,3-bis- (4-hydroxy-3-t-
[Butylphenyl) butyric acid] glycol ester, dilaurylthiodipropionate, triphenylphosphite and the like.

When an antioxidant is added, the amount added is usually from 0.001 to 1 in the paste.
% By weight.

To adjust the viscosity of the solution, an organic solvent may be added to the photosensitive paste of the present invention. The organic solvent used at this time includes 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 an organic solvent mixture containing at least one of these are used.

The refractive index of the organic component is the refractive index of the organic component in the paste at the time when the photosensitive component is exposed to light. In other words, when the paste is applied and the exposure is performed after the drying step, it refers to the refractive index of the organic component in the paste after the drying step. For example, there is a method of applying a paste on a glass substrate, drying the paste at 50 to 100 ° C. for 1 to 30 minutes, and measuring the refractive index.

The measurement of the refractive index in the present invention is preferably performed by a generally performed ellipsometry method or V-block method, and the measurement is performed at the wavelength of the light to be exposed, which is accurate for confirming the effect. In particular, it is preferable to measure with light having a wavelength in the range of 350 to 650 nm. Further, it is preferable to measure the refractive index at the i-line (365 nm) or the g-line (436 nm).

Further, in order to measure the refractive index after the organic component is polymerized by light irradiation, it can be measured by irradiating only the organic component with the same light as when irradiating light in the paste.

As the sensitizer, those having absorption at the exposure wavelength are used. In this case, the refractive index becomes extremely high near the absorption wavelength. In addition, the refractive index of the organic component can be improved. In this case, the sensitizer may be added in an amount of 3 to 10% by weight.

The photosensitive paste is usually prepared by mixing various components such as inorganic fine particles, an ultraviolet absorber, a photosensitive polymer, a photosensitive monomer, a photopolymerization initiator, a glass frit and a solvent so as to have a predetermined composition. The mixture is uniformly mixed and dispersed with three rollers or a kneading machine.

The viscosity of the paste is appropriately adjusted by the addition ratio of inorganic fine particles, a thickener, an organic solvent, a plasticizer, a suspending agent, etc., but the range is from 2000 to 200,000 cp.
s (centipoise). For example, when applying to a glass substrate by a spin coating method other than the screen printing method, 200 to 5000 cps is preferable. In order to obtain a film thickness of 10 to 20 μm by applying once by the screen printing method, 5
10,000 to 200,000 cps is preferable.

Next, an example of performing pattern processing using a photosensitive paste will be described, but the present invention is not limited to this.

A photosensitive paste is applied entirely or partially on a glass substrate, a ceramic substrate, or a polymer film. As the application method,
Methods such as screen printing, a bar coater, a roll coater, a die coater, and a blade coater can be used. The coating thickness is determined by the number of coatings, screen mesh,
It can be adjusted by choosing the viscosity of the paste.

Here, when applying the paste on the substrate,
Surface treatment of the substrate can be performed to enhance the adhesion between the substrate and the coating film. Examples of the surface treatment liquid include silane coupling agents such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and tris-silane.
(2-methoxyethoxy) vinylsilane, γ-glycidoxypropyltrimethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, γ (2-aminoethyl) aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and the like, or organic metals such as organic titanium, organic aluminum and organic zirconium. The silane coupling agent or the organic metal is dissolved in an organic solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol or the like.
Use the one diluted to a concentration of 1 to 5%. Next, after applying this surface treatment liquid uniformly on the substrate with a spinner or the like, 8
Surface treatment can be performed by drying at 0 to 140 ° C. for 10 to 60 minutes.When applied on a film, after drying on the film, performing the next exposure step,
There is a method in which an exposure step is performed after the film is pasted on a glass or ceramic substrate.

After application, exposure is performed using an exposure apparatus. The exposure is generally performed by a mask exposure using a photomask, as is performed by ordinary photolithography. As the mask to be used, either a negative type or a positive type is selected depending on the type of the photosensitive organic component.

Further, a method of directly drawing with a red or blue laser beam without using a photomask may be used.

As an exposure apparatus, a stepper exposure machine, a proximity exposure machine, or the like can be used. In the case of performing a large-area exposure, after applying a photosensitive paste on a substrate such as a glass substrate, and performing the exposure while transporting, it is possible to expose a large area with an exposure machine having a small exposure area. it can.

The active light source used at this time is, for example,
Visible light, near-ultraviolet light, ultraviolet light, electron beam, X-ray, laser light, etc. are preferable. Among them, ultraviolet light is preferable. Etc. can be used. Among these, an ultra-high pressure mercury lamp is preferred.
Exposure conditions vary depending on the coating thickness, but 1 to 100 mW
Exposure is performed for 0.5 to 30 minutes using an ultra-high pressure mercury lamp having an output of / cm @ 2.

By providing an oxygen shielding film on the surface of the applied photosensitive paste, the pattern shape can be improved. As an example of the oxygen shielding film, a film of polyvinyl alcohol (PVA) or cellulose, or a film of polyester or the like can be given.

The PVA film is formed by uniformly applying an aqueous solution having a concentration of 0.5 to 5% by weight on a substrate by a method such as a spinner and then drying at 70 to 90 ° C. for 10 to 60 minutes to evaporate water. Let me do it. In addition, it is preferable to add a small amount of alcohol to the aqueous solution because the coatability with the insulating film is improved and the evaporation is facilitated. A more preferred solution concentration of PVA is 1 to 3% by weight. Within this range, the sensitivity is further improved. The reason why the sensitivity is improved by the PVA application is presumed as follows. That is, when the photosensitive component undergoes a photoreaction, the presence of oxygen in the air is considered to hinder the photocuring sensitivity, but the presence of a PVA film is considered to improve the sensitivity during exposure because excess oxygen can be blocked. .

When a transparent film of polyester, polypropylene, polyethylene, or the like is used, there is a method in which these films are attached to the photosensitive paste after application.

After the exposure, development is carried out using the difference in solubility between the photosensitive portion and the non-photosensitive portion in the developing solution. In this case, the development is performed by an immersion method, a shower method, a spray method, or a brush method.

As the developer used, an organic solvent in which the organic components in the photosensitive paste can be dissolved can be used. Water may be added to the organic solvent as long as the solvent does not lose its solubility. When a compound having an acidic group such as a carboxyl group is present in the photosensitive paste, development can be performed with an aqueous alkali solution. As the alkaline aqueous solution, a metallic alkaline aqueous solution such as sodium hydroxide, sodium carbonate, calcium hydroxide aqueous solution, etc. can be used, but it is preferable to use an organic alkaline aqueous solution since the alkaline component can be easily removed during firing.

As the organic alkali, an amine compound can be used. Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, diethanolamine and the like. The concentration of the alkaline aqueous solution is usually 0.01 to 10% by weight, more preferably 0.1 to 5% by weight. If the alkali concentration is too low, the soluble portion is not removed, and if the alkali concentration is too high, the pattern portion may be peeled off and the non-soluble portion may be corroded, which is not preferable. The development temperature during development is preferably from 20 to 50 ° C. from the viewpoint of process control.

Next, firing is performed in a firing furnace. The firing atmosphere and temperature vary depending on the type of the paste and the substrate, but firing is performed in an atmosphere of air, nitrogen, hydrogen, or the like. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used.

In the case of pattern processing on a glass substrate,
The calcination is carried out at a temperature of 540 to 610 ° C. for 10 to 60 minutes.

A heating step at 50 to 300 ° C. may be introduced during the above-mentioned steps of coating, exposure, development and baking for the purpose of drying and preliminary reaction.

[0102]

The present invention will be specifically described below with reference to examples. However, the present invention is not limited to this. The concentrations (%) in Examples and Comparative Examples are% by weight unless otherwise specified.

Example 1 A solvent (γ-butyrolactone) and a polymer were mixed to form a 40% solution, and heated to 60 ° C. with stirring to dissolve all the polymers uniformly.

The polymer is 40% methacrylic acid (M
AA), a weight average molecular weight obtained by subjecting a copolymer consisting of 30% methyl methacrylate (MMA) and 30% styrene (St) to an addition reaction of 0.4 equivalent of glycidyl methacrylate (GMA) to a carboxyl group. 43
000, a photosensitive polymer having an acid value of 95 was used.

Next, the solution was cooled to room temperature, and a photosensitive monomer, a photopolymerization initiator, a sensitizer and the like were added at the ratios shown in Table 1 and dissolved. Thereafter, this solution was filtered using a 400-mesh filter to produce an organic vehicle.

Next, sudan (an azo organic dye) was weighed to the glass powder so as to be in parts by weight shown in Table 1. Sudan is dissolved in acetone, a dispersant is added, and the mixture is uniformly stirred with a homogenizer. Glass powder is added to the solution, and the mixture is uniformly dispersed and mixed. And the acetone was evaporated. In this way, a powder was obtained in which the surface of the glass powder was uniformly coated with a film of an ultraviolet absorbent composed of an organic dye (so-called capsule treatment).

The glass powder was Li ₂ O 9%, SiO ₂ 2
2%, B ₂ O ₃ 33%, BaO 4%, Al ₂ O ₃ 23
%, ZnO 2%, and MgO 7%. The glass powder was made into a fine powder in advance using an attractor, and a non-spherical powder having an average particle size of 2.6 μm was used. g
The measured refractive index at the line (436 nm) was 1.59.

The organic vehicle and the glass powder to which the ultraviolet absorber was added were added so as to have the composition shown in Table 1, and 3
The photosensitive paste was prepared by mixing and dispersing with this roller.

This photosensitive paste was uniformly applied on a 100 mm square soda lime glass substrate by screen printing using a 325 mesh screen. Coating and drying were repeated several times or more in order to avoid generation of pinholes and the like in the coating film, and the film thickness was adjusted. Drying was performed at 80 ° C. for 10 minutes. Then, it was kept at 80 ° C. for 1 hour and dried.

Subsequently, using a negative-type chromium mask having a pitch of 150 μm, the surface was exposed to ultraviolet light from an upper surface with an ultra-high pressure mercury lamp of 50 mJ / cm ² output. The exposure amount was 1 J / cm ² .

Next, a 0.3% by weight aqueous solution of monoethanolamine kept at 35 ° C. was developed by applying a shower for 110 seconds, followed by washing with water using a shower spray, and a space portion not cured by light. Was removed to form a stripe-shaped partition on the glass substrate.

The glass substrate on which the partition walls were formed as described above was baked at 570 ° C. for 60 minutes in air to form insulating partition walls.

The sectional shape of the formed partition wall was observed with a scanning electron microscope, the half width was measured, and the average value of three samples was calculated. In addition, the falling and peeling before baking and the peeling after baking were evaluated. further,
The aperture ratio of each partition was defined as 1- (half width / pitch) and calculated.

Table 2 shows the results. There was no peeling, falling or disconnection before and after firing, and the coating uniformity of the phosphor was excellent.

Example 2 The composition of the photosensitive paste was changed as shown in Table 1, except that the exposure amount was 1.2 J / cm ² and the developing time was 85 seconds.
A study was conducted in the same manner as in Example 1. The composition of the glass powder is Li ₂ O 7%, SiO ₂ 23%, B ₂ O ₃ 33%,
BaO 4%, Al ₂ O ₃ 20%, ZnO 3%, Mg
A non-spherical powder with 10% O and an average particle size of 2.6 μm was used. The firing conditions were 560 ° C. for 60 minutes. Table 2 shows the results.

Example 3 The procedure of Example 1 was repeated, except that the composition of the photosensitive paste was changed as shown in Table 1 and the development time was changed to 100 seconds.
Study was carried out. The firing conditions were 565 ° C. for 60 minutes. The same glass powder as in Example 1 was used. Table 2 shows the results.

Example 4 The mask line width was changed as shown in Table 2, the composition of the photosensitive paste was changed as shown in Table 1, the exposure was 1.3 J / cm ² , and a 0.5% aqueous solution of monoethanolamine was developed. A study was conducted in the same manner as in Example 1 except that the liquid was used and the development time was changed to 70 seconds. The firing condition was 570 ° C. for 30 minutes.

The same glass powder as in Example 1 was used. A non-spherical powder having an average particle size of 3.2 μm was used.
Table 2 shows the results.

Comparative Example 1 The mask line width was set as shown in Table 2, the exposure amount was 2.5 J / cm ² ,
The study was conducted in the same manner as in Example 1 except that the developing time was 90 seconds. The composition of the glass powder was the same as in Example 1, but the average particle size was 3.2 μm. The firing conditions were 570 ° C. for 60 minutes. Table 2 shows the results.

The obtained partition walls had a residual film, and had a trapezoidal shape.

Comparative Example 2 A mask line width was changed as shown in Table 2, the composition of the photosensitive paste was changed as shown in Table 1, the exposure amount was changed to 1.1 J / cm ² , and the developing time was changed to 210 seconds. In the same manner as in Example 1,
Study was carried out.

The same glass powder as in Example 1 was used. Table 2 shows the results. The partition had a constricted shape at the root, and collapsed and peeled before firing, and also peeled after firing, and many breaks were observed. Further, the application of the phosphor was not successful due to the constriction, and the phosphor was protruded from the pattern. Although firing was performed at 570 ° C. for 30 minutes, the partition walls were peeled off, and the shape of the partition walls after firing could not be measured.

Example 5 Except that the mask line width was changed as shown in Table 2 and the composition of the photosensitive paste was changed as shown in Table 1, the exposure amount was changed to 1.2 J / cm ² , and the developing time was changed to 110 seconds. The study was conducted in the same manner as in Example 1. The same glass powder as in Example 1 was used. The firing condition was 560 degrees for 15 minutes. Table 2 shows the results.

Although the obtained partition wall had a good shape, it was insufficient in hardness and adhesion, and collapsed when scratched with a spatula.

Example 6 The procedure was performed except that the mask line width was changed as shown in Table 2, the composition of the photosensitive paste was changed as shown in Table 1, the exposure amount was 1.4 J / cm ² , and the developing time was 140 seconds. The study was conducted in the same manner as in Example 1. The same glass powder as in Example 1 was used. The firing conditions were 580 ° C. for 15 minutes. Table 2 shows the results.

Although the obtained partition walls were generally good in shape, the tops were rounded and the height varied, making them somewhat unsuitable for panel formation.

[0127]

[Table 1] Abbreviations in the table are shown below.

Sudan: azo organic dye, chemical formula C ₂₄ H
₂₀ N ₄ O, molecular weight 380.45 monomer (1); GX

Embedded image Monomer (2); D400

Embedded image Initiator: 2-benzyl-2 dimethylamino-1- (4
-Morpholinophenyl) -butanone-1 sensitizer; 2,4-diethylthioxanthone plasticizer; dibutyl phthalate (DBP)

[Table 2]

[0129]

By adopting the manufacturing method using the photomask of the present invention, a partition pattern with a small line width can be formed. Further, by using the mask according to the present invention, it is possible to extremely easily form the partition walls without disturbing the width and the skirt, and achieve high definition, high aspect ratio, and high precision. As a result, the aperture ratio of the screen can be increased, and a plasma display with high brightness, high definition, high display quality, and high density display can be provided.

Claims (9)

[Claims] A photosensitive glass paste containing a photoreactive organic component and a glass powder as essential components on a glass substrate, and exposing, developing and baking using a photomask, followed by partitioning of the plasma display panel. When manufacturing
A method for manufacturing a plasma display panel, wherein a line width L1 of a photomask satisfies the following expression with respect to a line width L2 of a partition pattern before firing. L2 / L1 = 1.1 to 5 2. The method according to claim 1, wherein a line width L3 of the partition wall after firing satisfies the following expression with respect to a line width L2 of the partition wall pattern before firing. L3 / L2 = 0.6-0.85 3. A method for manufacturing a plasma display, wherein a line width L1 of a photomask satisfies the following expression with respect to a line width L3 of a partition wall after baking. L3 / L1 = 0.8-3.5 4. The method for manufacturing a plasma display panel according to claim 1, wherein the photoreactive organic component is a photoinsolubilizing resin. 5. The pitch of the partition walls after firing is 100 to 160 μm.
4. The method for manufacturing a plasma display panel according to claim 1, wherein m, the line width of the partition after firing is 15 to 60 [mu] m, and the height of the partition after firing is 100 to 220 [mu] m. 6. The method of manufacturing a plasma display panel according to claim 1, wherein the refractive index of the glass powder is 1.5 to 1.65. 7. The method according to claim 1, wherein the glass powder contains 2 to 15% by weight of at least one of lithium oxide, sodium oxide and potassium oxide. 8. The method according to claim 7, wherein the glass powder has the following composition. Lithium oxide: 2 to 10 parts by weight Silicon oxide: 10 to 50 parts by weight Boron oxide: 20 to 40 parts by weight Barium oxide: 2 to 15 parts by weight Aluminum oxide: 6 to 25 parts by weight 9. The method of manufacturing a plasma display panel according to claim 1, wherein the photosensitive glass paste contains 0.05 to 1 part by weight of the ultraviolet light absorber based on the glass powder.