JP2001109145A - Pattern forming paste, member for display and display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive paste with which patterning with a high aspect ratio and high precision can be attained and in which peeling is not caused in baking. SOLUTION: The pattern forming paste consists of 50-95 wt.% inorganic fine particles and 5-50 wt.% organic component containing a lubricant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paste used for forming a pattern and a method for manufacturing a display using the same, such as manufacturing various displays including a plasma display, a plasma addressed liquid crystal display, and a field emission display. Used for pattern processing.

[0002]

2. Description of the Related Art In recent years, miniaturization and high definition of displays have been advanced, and accordingly, improvement of pattern processing technology has been desired. For example, a screen printing method, a sand blast method, a photosensitive paste method, a mold transfer method, and the like are known for forming a partition wall of a back plate that is a member of a plasma display. Of these, a screen printing method such as a screen printing method is known. Practical use of the photosensitive paste method, which does not define the limit of high definition by the mesh of the plate and can simplify the process, is essential. The partition wall forming step using the photosensitive paste method is performed, for example, as follows. A desired pattern is obtained by applying and drying a photosensitive paste on a substrate, exposing it to a pattern through a photomask, and removing an unexposed portion by development. Finally, the resulting pattern is fired to burn off organic components to form barriers consisting essentially of only inorganic components. Here, in the firing step, defects such as peeling, chipping, and cracking of the pattern have occurred,
There is an urgent need to eliminate these defects and bring the yield close to 100%.

[0003] As a method of eliminating the peeling of the pattern in the firing step, for example, Japanese Patent Application Laid-Open No. H11-135025 discloses a method in which the end of the pattern in the firing is bounced and peeled during firing by forming an inclination at the longitudinal end of the pattern. Means for suppressing are disclosed. However, in this case, there is room for improvement in that a processing step for inclining the longitudinal end of the pattern is required.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to enable pattern processing with a high aspect ratio and high definition,
Another object of the present invention is to provide a paste which does not cause pattern peeling during firing without adding a special step.

[0005]

That is, the present invention provides a 50
A pattern forming paste comprising -95% by weight of inorganic fine particles and 5-50% by weight of an organic component, wherein the organic component contains a lubricant.

Further, the present invention comprises 50 to 95% by weight of inorganic fine particles and 5 to 50% by weight of an organic component, wherein the organic component is a fatty acid amide, a fatty acid ester, an aliphatic hydrocarbon,
A paste for forming a pattern, comprising at least one compound selected from higher fatty acids, higher alcohols and fatty acid metal salts.

Further, the present invention provides a member for a display and a member for a plasma display, which are manufactured using the above-mentioned paste for forming a pattern.

The present invention also provides a display manufactured using the above-mentioned display member.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the paste of the present invention will be described.

[0010] The pattern forming paste of the present invention comprises 50
It is composed of -95% by weight of inorganic fine particles and 5-50% by weight of an organic component. When the amount of the inorganic fine particles is less than 50% by weight, coloring or insulation failure occurs due to insufficient binder removal at the time of baking, and the shrinkage is so large that the inorganic fine particles are easily peeled off from the substrate. On the other hand, when the content of the inorganic fine particles exceeds 95% by weight, it becomes difficult to handle the paste as a paste.

Further, the pattern forming paste of the present invention comprises:
It is important to include a lubricant. Lubricants are usually added to improve the fluidity and mold release properties of thermoplastic resins during heat molding, and include lubricants, brighteners, anti-adhesives, and release agents. What is called is also included. The properties and effects (lubricating effect) of the lubricant include the effect of depositing on the surface to reduce the frictional force with the contact object, and the effect of dissociating, for example, the aggregation of entangled molecules of polymer chains to slip. And the effect of giving flexibility and fluidity.

When this lubricant is added to a pattern forming paste such as a screen printing method, a sand blasting method, a photosensitive paste method, a mold transfer method, etc., in a firing step after the pattern formation, the pattern is peeled, cracked, disconnected, chipped or the like. Defects are suppressed. The mechanism is not clear,
For example, peeling is considered to occur due to a difference in shrinkage behavior between the lower part of the pattern that is in contact with the substrate and the upper part of the pattern that does not contact anything in the member manufacturing process.By adding a lubricant to the paste, the upper part of the pattern is removed. The shrinkage stress can be reduced, and the distortion in the vertical direction of the pattern is reduced,
It is assumed that peeling was suppressed.

Further, among these, when a lubricant is added to a photosensitive paste which forms a pattern through exposure and development, the effect of suppressing peeling becomes particularly remarkable. The following can be considered as a mechanism for suppressing peeling in the photosensitive paste method. That is, the pattern of the exposed photosensitive paste differs in the amount of active energy absorbed in the vertical direction, and the upper portion having a large amount of absorbed energy usually has a high crosslinking density. For this reason, it is considered that the contraction stress at the upper part of the pattern is increased and the pattern is separated due to the difference in the contraction behavior between the upper part and the lower part of the pattern. Here, when a lubricant is added to the photosensitive paste, the crosslinking density at the upper part of the pattern is reduced, and as a result, the balance of the shrinkage behavior of the upper part of the pattern and the lower part of the pattern is improved, and the peeling during firing, and the edge splash are suppressed. It is presumed that there is.

Therefore, in the present invention, a compound which is not generally classified as a lubricant can be used as a lubricant if it has such an effect.

Examples of the lubricant include fatty acid amides, fatty acid esters, aliphatic hydrocarbons, higher fatty acids, higher alcohols, fatty acid metal salts and the like.

Examples of the fatty acid amide include erucic acid amide, oleic acid amide, stearic acid amide, behenic acid amide, ethylenebisstearic acid amide, ethylenebisoleic acid amide, ethylenebiserucic acid amide, ethylenebislauric acid amide and the like. Is mentioned.

Examples of the fatty acid ester include methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl erucate, methyl behenate, butyl laurate, butyl stearate, isopropyl myristate, Isopropyl palmitate, octyl palmitate, octyl stearate, lauryl laurate, stearyl stearate, behenyl behenate, cetyl myristate, and the like.

Examples of the aliphatic hydrocarbon include liquid paraffin, natural paraffin, micro wax, polyethylene wax and the like.

Examples of the higher fatty acids include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, cerotic acid, montanic acid, melissic acid, and celloplastic acid.

Examples of higher alcohols include pentanol, octanol, dodecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, docosanol, tetracosanol, hexacosanol, heptacosanol, octacosanol, triacontanol Oleyl alcohol, linoleyl alcohol, linolenyl alcohol, and the like.

As fatty acid metal salts, lead stearate,
Examples include cadmium stearate, barium stearate, calcium stearate, zinc stearate, magnesium stearate, and laurate salts of these metals.

These can be used as a mixture of two or more kinds.

The amount of addition is preferably from 0.01 to 10% by weight, more preferably from 0.1 to 5% by weight, based on the total amount of the paste. By adding 0.01% by weight or more, pattern peeling after firing can be suppressed. Further, by setting the content to 10% by weight or less, the smoothness of the paste application surface can be maintained.

The pattern forming paste of the present invention will be described below by taking a photosensitive paste as an example.

In the photosensitive paste of the present invention, the organic components include photosensitive monomers, photosensitive oligomers, photosensitive polymers, light absorbers, sensitizers, sensitizing aids, polymerization inhibitors, binders, plasticizers, and the like. Additive components such as thickeners, organic solvents, antioxidants, dispersants, suspending agents and leveling agents can be added.

The photosensitive monomer used in the present invention includes:
Examples include compounds containing a carbon-carbon unsaturated bond as described below. For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, tert
-Butyl acrylate, n-pentyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxytriethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, Heptadecafluorodecyl acrylate, 2-hydroxyethyl acrylate, isobonyl acrylate, 2-hydroxypropyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluorope Chill 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, methoxylated cyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate , Triglycerol diacrylate, trimethylolpropane triacrylate, acrylamide,
Aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, benzyl acrylate,
1-naphthyl acrylate, 2-naphthyl acrylate, bisphenol A diacrylate, diacrylate of bisphenol A-ethylene oxide adduct, diacrylate of bisphenol A-propylene oxide adduct, thiophenol acrylate, benzyl mercaptan acrylate, and fragrances thereof A monomer in which 1 to 5 hydrogen atoms of a ring are substituted with chlorine or bromine atoms, or styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, chlorinated styrene,
Brominated styrene, α-methylstyrene, chlorinated α-methylstyrene, brominated α-methylstyrene, chloromethylstyrene, hydroxymethylstyrene, carboxymethylstyrene, vinylnaphthalene, vinylanthracene,
Vinyl carbazole and those obtained by changing some or all of the acrylate in the molecule of the compound to methacrylate, γ-methacryloxypropyltrimethoxysilane,
1-vinyl-2-pyrrolidone and the like. These monomers can be used alone or in combination of two or more.

An oligomer or polymer obtained by polymerizing at least one of these photosensitive monomers can also be used. Further, by copolymerizing an unsaturated acid such as an unsaturated carboxylic acid, the developability after exposure can be improved.

This oligomer or polymer can be used as a binder as it is, but is used as a photosensitive oligomer or photosensitive polymer having photosensitivity by adding a photoreactive group to a side chain or a molecular terminal. You can also. 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 includes an ethylenically unsaturated compound having a glycidyl group or an isocyanate group, a mercapto group, an amino group, a hydroxyl group, and a carboxyl group in the polymer, acrylic acid chloride, and methacrylic acid. There is a method of making an acid chloride or allyl chloride by 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 crotonate, glycidyl ether isocrotonic acid, and the like. 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 1 molar equivalent based on the mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. It is preferable to add them.

In the present invention, it is effective to add an antioxidant. The antioxidant has a radical chain inhibiting action, a triplet eliminating action, and a hydroperoxide decomposing action. Since the photosensitive paste for forming a pattern contains many inorganic fine particles in a dispersed state, light scattering inside the paste due to exposure light is unavoidable. Film formation). The walls of the pattern are desirably vertically cut and rectangular. Ideally, it is dissolved in the developer below a certain exposure amount, and insoluble in the developer above it. In other words, it is preferable that even if a small amount of light is exposed to the scattered light, it is not dissolved in a developing solution and the pattern shape is not thickened or buried between patterns.

When an antioxidant is added to the photosensitive paste, extra light reactions due to scattered light are suppressed by capturing radicals or returning the excited photopolymerization initiator or sensitizer to the ground state. Is done. Therefore, a photoreaction occurs rapidly at an exposure amount that cannot be suppressed by the antioxidant,
The contrast between dissolution and insolubility in the developer can be increased.

Specifically, p-benzoquinone, naphthoquinone, p-xyloquinone, p-toluquinone, 2,6-dichloroquinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicaproxy-p-benzoquinone, hydroquinone , Pt-butylcatechol, 2,5-dibutylhydroquinone, mono-t-butylhydroquinone, 2,5
-Di-t-amylhydroquinone, di-t-butyl-p-
Cresol, hydroquinone monomethyl ether, α-naphthol, hydrazine hydrochloride, trimethylbenzylammonium chloride, trimethylbenzylammonium oxalate, phenyl-β-naphthylamine, parabenzylaminophenol, di-β-naphthylparaphenylenediamine, dinitrobenzene, trinitrobenzene Nitrobenzene,
Picric acid, quinone dioxime, cyclohexanone oxime, pyrogallol, tannic acid, triethylamine hydrochloride, dimethylaniline hydrochloride, cuperone, (2,2 ′
-Thiobis (4-t-octylphenolate) -2-ethylhexylaminonickel- (II), 4,4'-thiobis- (3-methyl-6-t-butylphenol),
2,2'-methylenebis- (4-methyl-6-t-butylphenol), 2,2'-thiobis- (4-methyl-
6-t-butylphenol), triethylene glycol-bis [3- (t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [(3,5-di-t- Butyl-4-hydroxyphenyl) propionate], 1,2,3-trihydroxybenzene, and the like, but are not limited thereto. In the present invention, one or more of these can be used.

The amount of the antioxidant added is 0.1 to 30% by weight, more preferably 0.5 to 20% by weight in the photosensitive paste.
% By weight. By making it 0.1% by weight or more,
The contrast of dissolution and insolubility in the developer can be increased, and by setting the content to 30% by weight or less, the sensitivity of the photosensitive paste is not reduced, so that a large amount of exposure is required and the polymerization degree is low. There is no possibility that the pattern shape cannot be maintained due to the rise.

To adjust the viscosity of the solution, an organic solvent may be added to the photosensitive paste of the present invention. As the organic solvent used at this time, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone,
Dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, γ
-Butyrolactone, N-methylpyrrolidone, 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 inorganic fine particles in the photosensitive paste of the present invention include glass powder and ceramic fine particles.
Particularly useful is the case where glass powder is used.

As the glass powder, the glass transition point 430
When the paste contains glass powder having a softening point of ５００500 ° C. and a softening point of 470-580 ° C. in an amount of 50% by weight or more, pattern processing can be suitably performed on a substrate used for a normal display. The refractive index of the glass powder is 1.5 to
By setting the ratio to 1.65, the refractive index of the glass powder and the refractive index of the organic component are matched, and light scattering is suppressed, whereby highly accurate pattern processing can be performed.

As the glass powder having such properties, for example, a combination of the following compositions can be preferably used. Lithium oxide: 3 to 10% by weight Silicon oxide: 10 to 30% by weight Boron oxide: 20 to 40% by weight Barium oxide: 2 to 15% by weight Aluminum oxide: 10 to 25% by weight

Among these, it is particularly useful to contain lithium oxide, and lithium oxide is contained in an amount of 3 to 10% by weight.
By using the contained glass powder, not only is it easy to control the thermal softening temperature and thermal expansion coefficient, but also the average refractive index of the glass can be lowered, so that the difference in the refractive index from the organic component can be easily reduced. . The amount of the alkali metal oxide added is preferably 10% by weight or less, more preferably 8% by weight, in order to improve the stability of the paste.
% By weight or less.

It is preferable that silicon oxide is blended in the range of 10 to 30% by weight, and when it is 10% by weight or more, the denseness, strength and stability of the glass layer can be obtained, and the coefficient of thermal expansion has a desired value. Since it can be within the range, no mismatch with the glass substrate occurs. Further, when the content is 30% by weight or less, there is an advantage that the softening point is lowered, and baking on a glass substrate becomes possible.

It is preferable that boron oxide is blended in the range of 20 to 40% by weight. When the content is 40% by weight or less, the stability of the glass can be maintained. Boron oxide dissolves glass powder at a temperature of about 800 to 1200 ° C., and impairs electrical, mechanical and thermal properties such as electrical insulation, strength, coefficient of thermal expansion, and denseness of an insulating layer even when silicon oxide is large. Baking temperature 540-61 to prevent
It is blended to control the temperature within the range of 0 ° C. If the content of boron oxide is too small, the strength of the insulating layer tends to decrease, and the stability of the glass tends to decrease.

It is preferable that barium oxide is blended in the range of 2 to 15% by weight. When the content is 2% by weight or more, it is easy to control the glass baking temperature and the electrical insulation. Further, when the content is 15% by weight or less, stability and denseness of the glass layer can be maintained.

It is preferable that aluminum oxide is blended in the range of 10 to 25% by weight. Aluminum oxide is added to increase the strain point of the glass. When the content is 10% by weight or more, the strength of the glass layer is improved. By setting the content to 25% by weight or less, the glass can be easily baked on a glass substrate without the heat-resistant temperature of the glass becoming too high, and a dense insulating layer can be obtained at a temperature of 600 ° C. or less. .

In a glass powder, sodium oxide,
Potassium oxide, yttrium oxide, and the like deteriorate the discharge characteristics of the plasma, so that the content thereof is preferably set to 5% by weight or less, and further preferably, these are not contained.

As a method for producing the glass powder, for example, raw materials such as lithium oxide, silicon oxide, boron oxide, barium oxide, and aluminum oxide are mixed so as to have a predetermined composition and melted at 900 to 1200 ° C. It is quenched, made into a glass frit, and then crushed to a fine powder of 1 to 5 μm. As a raw material, a high-purity carbonate, oxide, hydroxide, or the like can be used. Also, depending on the type and composition of the glass powder, the use of a powder prepared uniformly by a sol-gel method using an ultra-high purity alkoxide or organometallic material of 99.99% or more will result in a high electrical resistance and a high density. It is preferable because a high-strength insulating layer having few pores can be obtained.

The particle diameter of the glass powder used in the above is selected in consideration of the shape of the pattern to be produced, and the powder has a particle diameter of 50% by weight (average particle diameter) of 2 to 2.
It is preferably 3.5 μm and the top size is 15 μm or less. Furthermore, a 10% by weight particle size is 0.6 to 1.5 μm.
m, 90% by weight particle size 4-8 μm, specific surface area 1.5-
It is preferred to have 2.5 m ² / g. More preferably, the average particle size is 2.5 to 3.5 μm, and the specific surface area is 1.7.
２2.4 m ² / g. Within this range, light is sufficiently transmitted at the time of exposure to ultraviolet light, and a partition pattern with a small line width difference between the upper and lower portions can be obtained. Further, by setting the average particle diameter to 2.0 μm or more and the specific surface area to 2.5 m ² / g or less, the powder does not become too fine, and it is possible to prevent light from being scattered at the time of exposure and hardening an unexposed portion. .

The photosensitive paste is usually made of an ultraviolet absorber,
Antioxidants, inorganic fine particles, photosensitive organic components, organic dyes,
Various components such as a dispersant, a light absorbing agent, and a solvent are blended so as to have a predetermined composition, and then uniformly mixed and dispersed with a three-roller or a kneader to produce.

The viscosity of the paste is appropriately adjusted by the addition ratio of inorganic fine particles, a thickener, an organic solvent, a plasticizer, an antisettling agent, etc., but the range is from 2000 to 200,000 cp.
s (centipoise). For example, when the coating on the substrate is performed by the spin coating method, 20
00 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, 50,000 to 2
100,000 cps is preferred. When using a blade coater method, a die coater method, or the like, 10,000 to 50,000 cps is preferable.

Next, the display member of the present invention, the display, and the method of manufacturing the display member will be described in accordance with the procedure for manufacturing a plasma display. However, the present invention is preferably applied to various other displays such as a plasma addressed liquid crystal display and a field emission display.

The substrate of the back plate of the plasma display is
General soda lime glass, glass obtained by annealing soda lime glass, or high strain point glass (PD-200 manufactured by Asahi Glass Co., Ltd.) can be used. Those having a thickness of 1 to 5 mm can be preferably used.

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, tris (2-methoxyethoxy) vinylsilane, γ-glycidoxypropyltrimethoxysilane, γ- (methacrylic acid). Roxypropyl) trimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like, or an organic metal such as , Organic titanium,
Organic aluminum, organic zirconium and the like. A silane coupling agent or an organic metal diluted with an organic solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl alcohol, ethyl alcohol, propyl alcohol, or butyl alcohol to a concentration of 0.1 to 5% is used. Used.
Next, this surface treatment liquid is uniformly applied on a substrate by a spinner or the like, and then dried at 80 to 140 ° C. for 10 to 60 minutes to perform surface treatment. @ An address electrode is formed on a glass substrate using a metal such as silver, aluminum, chromium, or nickel. As a method of forming, a method of pattern-printing a metal paste containing these metal powders and an organic binder as main components by screen printing, or applying a photosensitive metal paste using a photosensitive organic component as an organic binder, and applying a photo Pattern exposure is performed using a mask, and unnecessary portions are dissolved and removed in a developing step.
A photosensitive paste method of forming a metal pattern by heating and baking at 00 ° C. can also be used. In addition, an etching method in which a metal such as chromium or aluminum is sputtered on a glass substrate, a resist is applied, and the resist is subjected to pattern exposure / development, followed by etching to remove an unnecessary portion of the metal by etching. The electrode thickness is 1
It is preferably from 10 to 10 μm, more preferably from 2 to 5 μm. If the electrode is too thin, the resistance value tends to be large and accurate driving tends to be impossible. If the electrode is too thick, a large amount of material is required and the cost tends to be disadvantageous. The width of the address electrode is preferably from 20 to 200 μm, more preferably from 30 to 1 μm.
00 μm. If the address electrodes are too thin, the resistance value tends to be high and accurate driving tends to be difficult. If the address electrodes are too thick, the distance between adjacent electrodes is small, and short-circuit defects tend to occur. Further, the address electrodes are formed at a pitch corresponding to the display cell (the area where each RGB of a pixel is formed). 100 ~ 500 for normal PDP
In a high-resolution PDP, the pitch is preferably 100 to 250 μm.

Next, a dielectric layer is preferably formed so as to cover the electrodes. The dielectric layer can be formed by applying a glass paste obtained by kneading a pigment, a glass powder, an organic binder, and the like on the substrate on which the electrodes are formed, and then baking at 400 to 600 ° C. The thickness of the dielectric layer is 4 to 2
0 μm is preferred.

Next, a partition is formed on the dielectric layer or on the substrate on which the electrodes are formed. The height of the partition walls is preferably 80 μm or more after firing. By setting the thickness to 80 μm or more, it is possible to prevent the phosphor and the scan electrode from coming too close to each other, and to suppress the deterioration of the phosphor due to discharge. Partition pitch (P)
Of those, those with 100 μm ≦ P ≦ 500 μm are often used. 100μm ≦ P ≦ 250μ as high definition PDP
m, 300 μm ≦ P ≦ 500 μ as low definition PDP
m is used. By setting the thickness to 100 μm or more, it is possible to prevent a discharge space from being narrowed and obtain sufficient luminance.
By setting the thickness to 0 μm or less, the pixels become finer and a clear image display can be performed. By setting the thickness to 250 μm or less, a beautiful video at a high definition (HDTV) level can be displayed. The line width (L) of the partition is 10 μm ≦ L ≦ 50 μm as a half width in a high definition PDP and 40 in a low definition PDP.
It is preferable that μm ≦ L ≦ 120 μm. High definition P
By setting the diameter to 10 μm or more for DP and 40 μm or more for low-definition PDP, it is possible to prevent breakage when sealing the front plate and the back plate. In the case of a high-definition PDP,
In the case of a low-definition PDP, by setting the thickness to 120 μm or less, a large phosphor formation area can be obtained, and high luminance can be obtained.

The partition walls are formed by applying the above-mentioned photosensitive paste of the present invention, exposing, developing using the difference in solubility between the exposed portion and the unexposed portion in a developing solution, and then firing.

The application of the photosensitive paste can be performed by a general method such as a screen printing method, a bar coater method, a roll coater method, and a doctor blade method. The coating thickness can be determined in consideration of a desired height of the partition walls and a shrinkage ratio due to baking of the paste.

After application, exposure is performed using an exposure device. As an exposure apparatus, a proximity exposure machine or the like can be used. Also, when performing large area exposure,
After applying the photosensitive paste on the substrate, by performing exposure while transporting, with an exposure machine with a small exposure area,
A large area can be exposed. The active light used at this time is, for example, ultraviolet light, electron beam, X-ray, visible light, near-infrared light, etc., after exposure, using the difference in solubility between the exposed part and the unexposed part in the developing solution to perform development. In this case, the immersion method, the spray method, and the brush method are used. An organic solvent in which an organic component in the photosensitive paste can be dissolved is used as the developer. In addition, water may be added to the organic solvent as long as its solubility is not lost. When there is a compound having an acidic group such as a carboxyl group in the photosensitive paste,
It can be developed with an alkaline aqueous solution. As the alkaline aqueous solution, sodium hydroxide, sodium carbonate, calcium hydroxide aqueous solution and the like can be used, but it is preferable to use an organic alkaline aqueous solution since an alkaline component can be easily removed during firing.

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

The concentration of the aqueous alkali solution is usually 0.05 to 5
%, More preferably 0.1 to 1% by weight. If the alkali concentration is too low, it becomes difficult to remove the soluble portion, and if the alkali concentration is too high, the pattern tends to peel off or erode the non-soluble portion. 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 paste or substrate, but firing is performed in an atmosphere such as air, nitrogen, or hydrogen. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used.

The firing temperature is 400 to 1000 ° C. When processing a pattern on a glass substrate, 480 to 610
The firing is carried out at a temperature of 10 ° C. for 10 to 60 minutes.

After the partition walls are formed, a phosphor layer that emits light of each color of RGB is formed. By applying a phosphor paste containing a phosphor powder, an organic binder and an organic solvent as main components between predetermined partition walls, a phosphor layer can be formed. Examples of the method include a screen printing method in which a pattern is printed using a screen printing plate, a dispenser method in which a phosphor paste is pattern-discharged from the tip of a discharge nozzle, and a photosensitive phosphor in which a photosensitive organic component is used as an organic binder. A photosensitive paste method using a paste or the like can be employed.

If necessary, the substrate on which the phosphor layer is formed may be
By firing at 400 to 550 ° C., a back plate for a plasma display can be manufactured as an example of the display member of the present invention.

Next, a front plate for a plasma display can be manufactured by forming a transparent electrode, a bus electrode, a dielectric, and a protective film (MgO) on a substrate in a predetermined pattern. A color filter layer may be formed at a portion corresponding to the RGB phosphor layers formed on the back plate. Also,
In order to improve the contrast, a black stripe may be formed.

After sealing the back plate and the front plate thus obtained, helium and helium are added to the space formed between the substrates between the two members.
After charging a discharge gas composed of neon, xenon, or the like, a driving circuit is mounted, and a plasma display can be manufactured as an example of the display of the present invention.

[0063]

The present invention will be specifically described below with reference to examples. However, the present invention is not limited to this. The concentration (%) in the examples and comparative examples is% by weight.

(Examples 1 to 10) A mixture having the following composition was kneaded with three rollers. 1) Glass powder: 60 parts by weight 2) Polymer: 10 parts by weight 3) Monomer (described in Table 1): 10 parts by weight 4) Photopolymerization initiator ('Irgacure 369' (2-benzyl-2-dimethylamino-1) -(4-morpholinophenyl) butanone-1: manufactured by Ciba Specialty Chemicals)): 2 parts by weight 5) Solvent (γ-butyrolactone): 17 parts by weight 6) Lubricant (described in Table 1): 0.5 Parts by weight.

The above glass powder has a composition of Li ₂ O: 9%, SiO ₂ : 22%, Al ₂ O ₃ : 2 in terms of oxide.
_{3%, B 2 O 3:} 33%, BaO: 4%, ZnO: 2%,
MgO: 7% was used. This glass powder has an average refractive index of 1.586, a glass transition point and a softening point of 4 respectively.
76 ° C., 519 ° C., the average particle size is 2.6 μm.

As the above polymer, a weight average molecular weight of 30 in which 0.4 equivalent of glycidyl methacrylate is added to a carboxyl group of a copolymer composed of 40% methacrylic acid, 30% methyl methacrylate and 30% styrene.
000, a photosensitive polymer having an acid value of 100 was used.

The obtained paste was uniformly applied on a glass substrate on which electrodes and a dielectric layer had been formed by using a screen printing method. Coating and drying are repeated several times or more in order to avoid pinholes and the like on the coating film.
A sample of 00 μm was prepared. 80 drying during printing
C. for 10 minutes and finally dried at 80.degree. C. for 60 minutes.

Next, a photomask for pattern formation (striped pattern, pattern pitch 360 μm, line width 6
0 .mu.m) was 110 mJ / cm ² exposed through the (source: high pressure mercury lamp). At this time, in order to prevent the mask from being contaminated, a gap of 100 μm was provided between the mask and the coating film surface. Thereafter, development was performed by applying a 0.3% by weight aqueous solution of monoethanolamine kept at 35 ° C. in a shower for 150 seconds to form a stripe-shaped partition pattern on the substrate. Top width 85 to 95 μm, bottom width 11
A partition pattern having a thickness of 0 to 120 μm and a half width of 85 to 110 μm was obtained.

Subsequently, the partition pattern was baked at 580 ° C. for 20 minutes. After firing, the end of the partition is
Evaluation was made as to whether the film was peeled off. The results are shown in Table 1.

(Comparative Examples 1 to 3) A barrier rib pattern was formed and fired in the same manner as in Examples 1, 9, and 10 except that no fatty acid amide was added. Peeling occurred at the end of the partition.

[0071]

[Table 1]

(Embodiment 11) In the same manner as in Embodiment 1, the electrodes,
The paste used in Example 1 was dried to a thickness of 2 on a substrate on which a dielectric layer was formed by screen printing.
It was applied so as to be 00 μm.

Next, exposure was performed in the same manner as in Example 1 through a photomask for forming a partition pattern for a plasma display (striped pattern, pattern pitch: 360 μm, line width: 60 μm). Exposure is 120 mJ / cm
^{And 2} . Thereafter, development was performed by applying a 0.3% by weight aqueous solution of monoethanolamine kept at 35 ° C. in a shower for 150 seconds to form a stripe-shaped partition pattern on the substrate. Top width 89μm Bottom width 125μm
Was obtained.

The resulting partition was baked at 580 ° C. for 20 minutes. After firing, the pattern does not peel off and has a height of 150
A partition wall having a width of 72 μm, a top width of 72 μm, and a bottom width of 108 μm was obtained.

Next, a phosphor was applied between adjacent partition walls. The phosphor is applied in 256 holes (diameter: 130μ).
m) was formed by a dispenser method of discharging a phosphor paste from the tip of the nozzle formed. The phosphor has a thickness of 25 μm after firing on the side wall of the partition and a thickness of 25 μm after firing on the dielectric layer.
After coating to a thickness of μm, baking was performed at 500 ° C. for 10 minutes. Thus, a back plate of a plasma display was manufactured as the display member of the present invention.

Further, the produced front plate and back plate were sealed with a sealing glass, and a neon gas containing 5% of xenon was sealed so as to have an internal gas pressure of 66500 Pa. Further, a PDP was manufactured as a display of the present invention by mounting a driving circuit. The produced PDP was normally driven on the entire surface.

(Example 12) A field emission display was manufactured by sealing a back plate for fixing an electron source on which an electron-emitting device was formed, and a front plate on which a phosphor layer and a metal back were formed. Between the front plate and the back plate, a support frame and a partition wall (spacer) as an anti-atmospheric pressure support member were produced.

The paste used in Example 1 was applied to the entire surface of the substrate on which the surface conduction electron-emitting device and the inter-electrode wiring were formed by screen printing and dried, and this was repeated to form a coating film having a dry thickness of 200 μm. did. A photomask having a stripe-shaped opening having a width of 2 mm and a pitch of 1 cm was closely attached to the coating film, and irradiation was performed at 120 mJ / cm ² using a high-pressure mercury lamp. This process was repeated five times to form a 1.0 mm coating film.

Further, 200 μm was formed on the coating film in the same manner as described above.
m, and a photomask having an opening width of 1.6 mm was aligned in such a manner as to correspond to the first exposed portion, and exposed similarly. This process is repeated five more times, for a total of 2.0 mm
Was formed.

Further, on this coating film, 200 μm
It was applied and exposed to 120 mJ / cm ² using a photomask having an opening with a width of 1.2 mm. The coating film thus exposed is developed and developed by the same means as in the first embodiment.
After washing with water, a stripe-shaped partition (spacer) pattern having a height of about 2.2 mm and a three-stage cross section was formed.
This was fired in air at 570 ° C. for 30 minutes to obtain a back plate for a field emission display. Peeling of the pattern after firing was not observed.

On the other hand, a front plate provided with a black matrix and a phosphor layer for emitting light in three primary colors and provided with a metal back was separately prepared and sealed with the back plate to obtain a field emission display.

The manufactured field emission display was normally driven.

[0083]

According to the photosensitive paste of the present invention, a pattern with a high aspect ratio and high definition can be processed in one processing step, and the pattern is peeled or cracked during firing. There is no. Thereby, the productivity of display members, circuit materials, and the like is improved.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA00 AA02 AA03 AB14 AC01 AD01 BC12 BC31 CC12 CC20 5C040 GF18 GF19 JA02 JA15 KA09 KA16 KA17 KB03 KB19 MA23 MA24

Claims (6)

[Claims] (1) 50 to 95% by weight of inorganic fine particles and 5 to 50% by weight.
A pattern-forming paste comprising an organic component in an amount of% by weight, wherein the organic component contains a lubricant. 2. 50 to 95% by weight of inorganic fine particles and 5 to 50% by weight.
At least one selected from fatty acid amides, fatty acid esters, aliphatic hydrocarbons, higher fatty acids, higher alcohols, and fatty acid metal salts.
A paste for forming a pattern, comprising a kind of compound. 3. The pattern forming paste according to claim 1, wherein the paste is cured by exposure. 4. A display member manufactured using the pattern forming paste according to claim 1. 5. A member for a plasma display manufactured using the pattern forming paste according to claim 1. 6. A display manufactured using the display member according to claim 4. Description: