JP2002049146A - Photosensitive paste and member for display using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive paste excellent in dispersion stability of a filler and to provide a member for a display having partition walls formed by good patterning by photolithography and excellent in display characteristics such as chromaticity, luminance and contrast. SOLUTION: The photosensitive paste has 0.1-150×10-4 S/m electric conductivity or 0.001-500 ppm chlorine ion concentration. The member for a display has partition walls formed using the photosensitive paste by photolithography.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive paste and a display member, and more particularly, to a photosensitive paste having improved dispersion stability of inorganic fine particles, and a plasma display panel using the photosensitive paste. PDP), plasma-addressed liquid crystal display (PALC), electron-emitting device (field emission or FE), or fluorescent display tube device (VFD)
Related to a display member.

[0002]

2. Description of the Related Art A display using a PDP, an electron-emitting device, and a fluorescent display device is a liquid crystal display (LCD).
Bright images are obtained compared to, and the viewing angle is wide.
In addition, since the demand for larger screens and higher definition can be met, the needs are increasing.

The electron-emitting devices include a thermionic electron-emitting device and a cold cathode electron-emitting device. A display using a cold cathode electron source displays an image by irradiating a phosphor with an electron beam emitted from an electron-emitting device to emit fluorescent light. In this device, the front glass substrate and the rear glass substrate are used with their respective functions. The rear glass substrate is provided with a plurality of electron-emitting devices and a matrix-like wiring for connecting the electrodes of those devices. Since these wirings intersect at the electrode portion of the electron-emitting device, an insulating layer for insulation is provided. Further, a partition wall (spacer) is formed between the two substrates as an anti-atmospheric pressure support member.

[0004] Unlike a CRT, the structure and electrical operation mechanism of a fluorescent display tube (VFD) excite a phosphor with a low-speed electron flow of several tens mA at a voltage of several tens of volts. Even in a display using such a VFD element, a partition wall such as a grid is formed to separate a light emitting region.

A PDP generates a plasma discharge between an anode electrode and a cathode electrode facing each other in a discharge space partitioned by partitions provided between a front glass substrate and a rear glass substrate, and is sealed in this space. The display is performed by irradiating the ultraviolet light generated from the flowing gas to the phosphor applied in the discharge space.

A plasma addressed liquid crystal display (PA)
LC) is a TFT-LCD in which the TFT (thin film transistor) array portion is replaced with a plasma channel, and has basically the same structure as the TFT-LCD except for the plasma portion. The plasma generating portion is separated by a partition having a height of about 200 μm and a pitch of about 480 μm. That is, each of the above various displays requires a partition. Hereinafter, on behalf of these various displays, P
Describe DP. Conventionally, in PDPs, partition walls are formed by screen-printing an insulating glass paste. However, in this method, there is a problem of alignment accuracy due to expansion and contraction of the screen plate. As a result, a large area and a high resolution cannot be obtained. As a method of solving such a problem, a method of forming a partition by a photolithography technique using a photosensitive paste is known.

The partition walls not only divide the light emitting area but also affect the display characteristics of the display such as light emission luminance and color purity. In order to improve the efficiency of light emission from the phosphor layer, there is a demand to increase the reflectance of the partition walls.
That is, if the light transmittance of the partition is high and the reflectance is low, the display light emitted from the phosphor layer applied to the side wall of the partition and the bottom surface between the partition is insufficiently reflected, and further, the fluorescent light between the adjacent partition is insufficient. Display light leaks from the body layer, and a display with high luminance and good color purity cannot be obtained. On the other hand, Japanese Patent Publication No. 6-44452 discloses formation of a partition wall using a mixture of glass powder and a filler having a different refractive index from the glass powder. It is unsuitable for forming a partition by a photolithography method using a method. Japanese Patent Application Laid-Open No. 8-138559 proposes a method of forming a reflective film on a surface of a formed partition wall for reflecting only light of a specific wavelength for display. However, there is a problem that the number of processes increases.

[0008] In order to improve light transmittance, inorganic fine particles having a small particle size can be used. However, if a large amount of chloride ions is present in the photosensitive organic component, the inorganic fine particles interact with the inorganic fine particles. Fine particles aggregate. On the other hand, as for ionic impurities, in particular, chloride ions and nitrate ions, JP-A-11-64619 discloses a total of 0.001 ppm to 150 ppm of chloride ions and nitrate ions.
A method of producing a color paste that contains all or part of chloride ions and nitrate ions by an ion exchange method is disclosed. However, with the technology disclosed here, the removal of chloride ions and nitrate ions is insufficient for high-viscosity pastes, and it is difficult to remove the ion-exchange resin after ion exchange. There is a disadvantage that the exchange resin inhibits the transmission of the exposure light, and a high-resolution partition wall having a high aspect ratio cannot be obtained by the photolithography method.

[0009]

SUMMARY OF THE INVENTION The present invention provides a photosensitive paste having excellent dispersion stability of inorganic fine particles and a method for producing the same, which solves such contradictory problems, and achieves good patterning by photolithography. It is an object of the present invention to provide a display member having formed partition walls and having excellent display characteristics such as chromaticity, emission luminance, and contrast.

[0010]

In order to solve the above problems, the present invention has the following arrangement. That is, the photosensitive paste of the first invention of the present invention is a photosensitive paste containing inorganic fine particles and a photosensitive organic component, and has an electric conductivity at 25 ° C. of 0.1 to 150 × 10 ⁻⁴ S / m. It is characterized by being within the range. Further, the photosensitive paste of the second invention is a photosensitive paste containing inorganic fine particles and a photosensitive organic component, wherein a chlorine ion concentration in the photosensitive paste is in a range of 0.001 to 500 ppm. And

Further, the display member of the present invention is characterized in that it has a partition wall formed using the photosensitive paste.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive paste of the present invention is used for the purpose of forming a pattern substantially consisting of an inorganic substance by baking after forming a pattern using a photolithography method, so that inorganic fine particles and a photosensitive organic compound are used. Contains ingredients.

The photosensitive paste of the first invention of the present invention has an electric conductivity at 25 ° C. within the range of 0.1 to 150 × 10 ⁻⁴ S / m from the viewpoint of dispersion stability of inorganic fine particles. It is. More preferably, 0.1 to 100 × 10 ⁻⁴ S / m
Is within the range. When the electric conductivity of the photosensitive paste is high, the fine dispersion of the inorganic fine particles is hindered by electric shielding,
This is because the aggregate of the inorganic fine particles hinders the transmission of the exposure light, and good patterning by the photolithography method cannot be obtained.

The photosensitive paste according to the second aspect of the present invention has a chlorine ion concentration of 0.001 to 500 in the photosensitive paste.
It must be in the ppm range. Here, the chlorine ion in the photosensitive paste refers to tetraethylbenzene ammonium chloride or the like. From the viewpoint of dispersion stability of the inorganic fine particles, the chlorine ion concentration in the photosensitive paste needs to be 500 ppm or less. More preferably, it is 300 ppm or less. By reducing impurity ions such as chlorine ions, inorganic fine particles in the photosensitive paste are stably and finely dispersed, so that the photosensitive paste coating film shows a high light transmittance, so that light transmittance during pattern exposure , High scattering, and excellent pattern formability. In addition, the chlorine ion concentration is 0.001 p.
pm or more. In order to further increase the efficiency, the content is preferably 0.1 ppm or more. Furthermore, in the photosensitive paste of the present invention, it is preferable that both the above-described conditions of the electric conductivity and the chloride ion concentration are satisfied.

Further, the inorganic fine particles in the photosensitive paste are
50 to 90 parts by weight of low melting glass powder, 0 to 30 parts by weight of filler A having an average particle size of 1.5 to 4 μm, and 3 of filler B having an average particle size of 0.003 to 0.02 μm
The amount of 50 to 50 parts by weight is preferable for decreasing the firing shrinkage, improving the strength of the formed partition wall, and making the partition wall opaque. By setting the low melting point glass of the inorganic fine particles to 50 parts by weight or more, a partition wall having high strength can be obtained without deformation of the partition wall shape in a firing step after pattern formation by a photolithography method. Furthermore, by setting the content to 90 parts by weight or less, the partition walls can be made of a low-melting glass and a filler, so that the firing shrinkage ratio decreases, the strength of the formed partition walls increases,
The partition walls can be made opaque.

The average particle diameter of the filler A is 1.5 μm.
By setting m or more, the effect of maintaining the shape of the partition wall during firing can be obtained. Further, since the filler A is not melted in the firing step, if it is more than 4 μm, the irregularities at the top of the formed partition walls tend to be large, which tends to cause problems such as crosstalk, which is not preferable.
Further, by setting the filler A to 30 parts by weight or less, a partition wall having high strength after firing can be obtained. Filler B
Is an inconsistent property that, when the average particle diameter is 0.003 μm or more, good light transmittance is exhibited in pattern formation by photolithography, and high reflectivity is exhibited as a partition after firing. Can be compatible. Further, in order to maintain good pattern formability of the photosensitive paste coating film, the upper limit of the average particle diameter is 0.0
It is preferable that the thickness be 2 μm or less. By setting the filler B to 3 parts by weight or more, it is possible to contribute to the improvement of the reflectance of the partition walls, and to 50% by weight or less as an upper limit for maintaining good pattern formability of the photosensitive paste coating film. preferable. It is more preferable to use both the filler A and the filler B described above.

The photosensitive paste is obtained by dispersing inorganic fine particles in a photosensitive organic component. In a coating film of the photosensitive paste, inorganic fine particles are present at a considerably high concentration in the photosensitive organic component layer. In order to form a pattern on such a coating film by photolithography, it is important to approximate at least the refractive index of each of the coexisting components. Since the average refractive index of the photosensitive organic component used is in the range of 1.4 to 1.7, the refractive index of the inorganic fine particles must be selected as close as possible to this range. The characteristics of the glass components composed of various oxides can be controlled by considering the composition thereof, and a low-melting glass powder having controlled thermal characteristics and refractive index can be used in the present invention. The low-melting glass powder has a refractive index of 1.45 to 1.65, a glass transition point of 400 to 550 ° C., and a softening point under load of 450 to 6.
Those having a temperature of 00 ° C are preferred. 450 ° C softening point under load
By doing so, the partition walls are not deformed in the steps after the member formation and the display formation, and the softening point under load is set to 600 ° C. or less, whereby the partition walls can be melted during firing and have high strength. The low-melting glass powder satisfying such characteristics preferably has the following composition in terms of oxide.

At least one of alkali metal oxides of lithium oxide, sodium oxide or potassium oxide is used, and the total amount is 3 to 15 parts by weight, and more preferably 3 to 10 parts by weight.
It is preferably in parts by weight.

The alkali metal oxide not only facilitates the control of the softening point under load and the coefficient of thermal expansion of the glass, but also reduces the refractive index of the glass. It is easy to reduce the size. When the total amount of the alkali metal oxides is 3 parts by weight or more, the effect of lowering the melting point of the glass can be obtained.
When the amount is not more than part by weight, the chemical stability of the glass can be maintained and the coefficient of thermal expansion can be suppressed to a small value. As the alkali metal, lithium is preferably selected in consideration of lowering the refractive index of the glass and preventing migration of ions.

The compounding amount of silicon oxide is preferably 5 to 30 parts by weight, more preferably 10 to 30 parts by weight. Silicon oxide is effective for improving the denseness, strength and stability of glass, and is also effective for lowering the refractive index of glass. The thermal expansion coefficient can be controlled to prevent separation due to mismatch with the glass substrate. When the amount is 5 parts by weight or more, the coefficient of thermal expansion is suppressed to a small value, and cracks do not occur when baked on a glass substrate. Further, the refractive index can be kept low. When the content is 30 parts by weight or less, the glass transition point and the softening point under load can be kept low, and the temperature for baking on a glass substrate can be lowered.

Boron oxide is a component necessary for lowering the melting point of glass that does not contain heavy metals such as lead.
Further effective in lowering the refractive index, 20 to 45 parts by weight,
Furthermore, it is preferable to mix in the range of 20 to 40 parts by weight. When the content is 20 parts by weight or more, the glass transition point and the softening point under load are suppressed to be low, and baking on a glass substrate is facilitated. Further, when the content is 45 parts by weight or more, the chemical stability of the glass can be maintained.

Preferably, at least one of barium oxide and strontium oxide is used, and the total amount is 2 to 15 parts by weight, more preferably 2 to 10 parts by weight. These components are effective in lowering the melting point of glass and adjusting the coefficient of thermal expansion, and are also preferable in terms of applying the baking temperature to the heat resistance of the substrate, electrical insulation, and stability and denseness of the formed partition walls. . When the content is 2% by weight or more, the effect of lowering the melting point can be obtained, and devitrification due to crystallization can be prevented. When the content is 15 parts by weight or less, the coefficient of thermal expansion can be kept small, and the refractive index can be kept small. Also, the chemical stability of the glass can be maintained.

Aluminum oxide has the effect of expanding the vitrification range and stabilizing the glass, and is also effective in extending the pot life of the paste. It is preferable to mix in the range of 10 to 25 parts by weight. By setting the content in this range, the glass transition point and the softening point under load can be kept low, and baking on a glass substrate can be facilitated.

Further, it is preferable that calcium oxide and magnesium oxide are blended to facilitate melting of the glass and to control the coefficient of thermal expansion. It is preferable to mix calcium oxide and magnesium oxide in a total amount of 2 to 15 parts by weight. When the total amount is 2 parts by weight or more, devitrification of the glass due to crystallization can be prevented, and when the total amount is 15 parts by weight or less, the chemical stability of the glass can be maintained.

Although not described in the above composition, zinc oxide is a component that lowers the melting point of the glass without greatly changing the coefficient of thermal expansion of the glass. If the amount is too large, the refractive index tends to increase. Therefore, the amount is preferably in the range of 1 to 20 parts by weight.

The low melting point glass powder used for the photosensitive paste has good filling properties and dispersibility at the time of forming the paste, is capable of being applied with a uniform thickness of the paste, and has good pattern forming properties. Has an average particle diameter of 1 to 4 μm
m, and the maximum particle diameter is preferably 35 μm or less. Glass powder having such a particle size distribution is excellent in terms of filling and dispersibility into paste, but in the case of low melting point glass powder, most of them are melted and integrated in a firing step, so that considerably large particles are used. Powders of a diameter are also acceptable.
Within this range, satisfying the filling property and dispersibility,
A photosensitive paste having excellent coating properties and pattern forming properties can be formed.

The filler A is added in an amount of 0 to 30 parts by weight in the inorganic fine particles, and preferably contains at least one selected from cordierite and high melting point glass powder. It is preferable that the refractive index of these fillers A matches the refractive index of the photosensitive organic component, similarly to the low melting point glass powder. As the high melting point glass powder, a glass transition point of 500 to 1200 ° C and a softening point under load of 550 to 1
It is preferable that the composition has a temperature of 200 ° C., and such a high melting point glass powder has a composition containing 15 parts by weight or more of silicon oxide and 15 parts by weight of aluminum oxide, respectively, and the total content thereof is 50 parts by weight or more. It is effective to obtain necessary thermal characteristics. The composition of the high melting point glass powder is not limited to this, but for example, the following oxide-converted composition can be used. Silicon oxide 15 to 50 parts by weight Boron oxide 5 to 20 parts by weight Barium oxide 2 to 10 parts by weight Aluminum oxide 15 to 50 parts by weight.

For example, the glass transition point is 38 parts by weight of silicon oxide, 10 parts by weight of boron oxide, 5 parts by weight of barium oxide, and 36% by weight of aluminum oxide, and contains calcium oxide, zinc oxide and magnesium oxide as other components little by little. The refractive index of the high melting point glass at 625 ° C. and the softening point under load of 750 ° C. is 1.59, which is equivalent to the refractive index of the low melting point glass preferably used in the present invention. Cordierite, another component of the filler A component, has a refractive index of 1.58 and is suitable.

As the filler B, at least one selected from the group consisting of alumina, zirconia, titania, ceria, yttria, tin oxide and silica is preferably used. The filler B has a higher refractive index than the low-melting glass powder, the filler A, and the photosensitive organic component used in the present invention. The fact that the refractive index is higher than that of low melting point glass or filler A means that such filler B
Will exhibit higher reflectivity, which is advantageous for forming a display with high brightness. But,
Since it is not preferable that there is a large refractive index difference in relation to the photosensitive organic component, in the present invention, the average particle diameter of the filler B is 3 which is the wavelength of light exposed for pattern formation.
0.003-0.02 μm smaller than 50-420 nm
(3 to 20 nm). In this way, even if the filler B is dispersed and present in the paste, it does not hinder pattern exposure and does not adversely affect pattern formation.

In order to stably and finely disperse the filler B in the photosensitive paste, it is preferable to perform a surface treatment with a surfactant. Specific examples of the surfactant include anionic surfactants such as ammonium lauryl sulfate, polyoxyethylene alkyl ether triethanolamine sulfate, cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride, lauryl dimethylamine oxide, lauryl Examples include amphoteric surfactants such as carboxymethylmethylhydroxymethylimidazolium betaine, and nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and sorbitan monostearate. In the present invention, the surfactant is not limited to these, and one or more surfactants can be used. The surfactant may be added at any time during or before or after the step of dispersing the filler B, but care must be taken since the dispersibility of the filler B may change depending on the time of the addition. On the other hand, when the partition pattern is baked, the presence of the filler B effectively acts on whitening of the partition, leading to an improvement in luminance and an improvement in color purity, and an improvement in display characteristics of the display. The cause of the effect of improving the reflectance of the partition walls by the addition of the filler B having such an average particle diameter is not necessarily clear, but is presumed as follows. That is, the oxide fine particles as the filler B having a fine average particle diameter aggregate in the firing step and have a particle diameter of 0.3 to 2 μm.
Constitute aggregated particles. Since the aggregated particles have a higher refractive index than the low-melting glass serving as the base, scattering by these aggregated particles becomes remarkable, improving the reflectance of the partition walls, and improving the efficiency of light emission from the phosphor layer. be able to. The preferred particle size of the aggregated particles is 0.5 to 1.0 μm
m. The particle diameter of such agglomerated particles refers to a diameter obtained by processing a photograph observed with an electron microscope and converting the image into a circle having the same area as the apparent area of the agglomerated particles. Observation and image processing were performed on 50 aggregated particles, and the average value was defined as the particle diameter of the aggregated particles.

The oxide fine particles as the filler B used in the present invention are microtrac particle size analyzer UPA150M
ODEL No. The average particle size measured using 9340 (Nikkiso Co., Ltd.) is preferably 0.003 to 0.02 μm. By using oxide fine particles having an average particle diameter in such a range, it is inconsistently required to exhibit good light transmittance in pattern formation by photolithography and to exhibit high reflectivity as a partition after firing. Characteristics can be compatible. By setting the average particle diameter of the filler B to 0.003 μm or more, it is possible to contribute to the effect of improving the reflectance of the partition walls, and the average particle diameter is set as an upper limit for maintaining good pattern formability of the photosensitive paste coating film. Is preferably 0.02 μm or less.

The photosensitive organic component in the photosensitive paste of the present invention is at least one selected from a reactive monomer, a reactive oligomer, and a reactive polymer, and if necessary, a binder polymer, a photopolymerization initiator, and a photoacid. Generators, photobase generators, sensitizers, sensitization aids, ultraviolet absorbers, organic dyes, dispersants, plasticizers, thickeners, organic solvents, acids, bases, anti-settling agents, antioxidants, etc. It is constituted by adding an additive component. Here, the reactivity of the reactive monomer, the reactive oligomer, and the reactive polymer means that when the photosensitive paste is irradiated with actinic light, the reactive monomer, the reactive oligomer, and the reactive polymer are photocrosslinked, It means that the chemical structure is changed through reactions such as photopolymerization, photodepolymerization, and photodenaturation.

The photosensitive organic component in the photosensitive paste of the present invention may contain a polymer having a carboxyl group in a side chain. Polymer having a carboxyl group in the side chain,
For example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, carboxyl group-containing monomers such as vinyl acetic acid or anhydrides thereof and methacrylic acid esters, acrylic acid esters, styrene, acrylonitrile, vinyl acetate, It is obtained by selecting a monomer such as 2-hydroxyacrylate and polymerizing it using an initiator such as azobisisobutyronitrile, but is not limited thereto.

The polymer having a carboxyl group in the side chain preferably has a resin acid value of 50 to 150 mgKOH / g. By setting the acid value to 150 mgKOH / g or less,
The development tolerance can be widened. In addition, the acid value is 50
When the concentration is not less than mgKOH / g, the solubility of the unexposed portion in the developing solution is not reduced, and therefore, it is not necessary to increase the concentration of the developing solution, the peeling of the exposed portion is prevented, and a high-definition pattern can be obtained. .

As the polymer having a carboxyl group in the side chain, a copolymer containing (meth) acrylic acid ester and (meth) acrylic acid as a copolymer component is preferably used because of its low thermal decomposition temperature during firing. Can be In particular, a styrene / methyl methacrylate / methacrylic acid copolymer is preferably used. Further, it is also preferable that the copolymer having a carboxyl group has an ethylenically unsaturated group in a side chain. Examples of the ethylenically unsaturated group include an acryl group, a methacryl group, a vinyl group and an allyl group. A method for adding such a side chain to a polymer is, for a mercapto group, an amino group, a hydroxyl group or a carboxyl group in the polymer, an ethylenically unsaturated compound having a glycidyl group or an isocyanate group, acrylic acid chloride, methacrylic acid chloride. Alternatively, there is a method of making an 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 crotonic acid, 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 mol based on the mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. It is preferable to add an amount. In order to obtain an appropriate amount of exposure, the amount of the polymer having a carboxyl group in the side chain is preferably 10 to 90 parts by weight in the organic component excluding the solvent. When a binder component is required, polyvinyl alcohol, polyvinyl butyral, a methacrylate polymer, an acrylate polymer, an acrylate-methacrylate copolymer, a butyl methacrylate resin, or the like may be used as the polymer. it can.

In the present invention, a monomer having an ethylenically unsaturated bond may be used if necessary. Examples of such a polymerizable monomer include a monomer having one or more photopolymerizable (meth) acrylate groups or allyl groups. Specific examples of these include alcohols (eg, ethanol, propanol, hexanol, octanol, cyclohexanol, glycerin,
Trimethylolpropane, pentaerythritol, etc.)
Acrylic or methacrylic esters, carboxylic acids (eg, acetic acid, propionic acid, benzoic acid, acrylic acid,
Reaction products of methacrylic acid, succinic acid, maleic acid, phthalic acid, tartaric acid, citric acid, etc.) with glycidyl acrylate, glycidyl methacrylate, allyl glycidyl, or tetraglycidyl methaxylylenediamine, amide derivatives (for example, acrylamide, Methacrylamide,
N-methylolacrylamide, methylenebisacrylamide, etc.), a reaction product of an epoxy compound and acrylic acid or methacrylic acid, glycidyl (meth) acrylate having an ethylenically unsaturated bond, (meth) acrylic acid chloride, (meth) acrylic anhydride Amine compounds and urethane compounds obtained by reacting a product with an amino compound. In the polyfunctional monomer, the unsaturated group may be a mixture of acryl, methacryl, vinyl, and allyl groups. These may be used alone or in combination.

The photopolymerization initiator used in the present invention is selected from those generating radical species. Examples of the photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-. 1-one, 4- (2-hydroxyethoxy) phenyl- (2-
(Hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenyl ketone, 1-phenyl-1,2
-Propanedione-2- (o-ethoxycarbonyl) oxime, 2-methyl- [4- (methylthio) phenyl]
-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl Ether, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4 '
-Methyl-diphenyl sulfide, alkylated benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-
N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethanaminium bromide, (4-benzoylbenzyl) trimethylammonium chloride, 2-hydroxy-3- (4-benzoylphenoxy) ) -N, N, N-Trimethyl-1-propenaminium chloride monohydrate, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2-hydroxy-3 -(3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N,
N, N-trimethyl-1-propanaminium chloride,
2,4,6-trimethylbenzoylphenylphosphine oxide, 2,2′-bis (o-chlorophenyl)-
4,5,4 ′, 5′-tetraphenyl-1,2-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, Methylphenylglyoxyester, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), diphenyl sulfide derivative, bis (η
5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 4,4-bis (dimethylamino) benzophenone, , 4-bis (diethylamino) benzophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 4-benzoyl-4-methylphenylketone, dibenzylketone, fluorenone, 2,3-diethoxyacetophenone, 2,
2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, benzylmethoxyethyl acetal, anthraquinone, 2-t-
Butylanthraquinone, 2-aminoanthraquinone, β
-Chloranthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone , 2
-Phenyl-1,2-butadione-2- (o-methoxycarbonyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, naphthalenesulfonyl chloride, quinoline sulfonyl chloride, N-phenylthioacrylic And photoreducing dyes such as 4,4-azobisisobutyronitrile, benzthiazole disulfide, triphenylphosphine, carbon tetrabromide, tribromophenylsulfone, benzoyl peroxide and eosin, methylene blue and ascorbic acid, Examples include a combination of a reducing agent such as ethanolamine. In the present invention, one or two of these are used.
More than one species can be used. The photopolymerization initiator is added in an amount of preferably 0.05 to 10 parts by weight, more preferably 0.1 to 10 parts by weight, based on the amount of the photosensitive organic component. By setting the amount of the photopolymerization initiator in this range, it is possible to obtain good photosensitivity while maintaining the remaining ratio of the exposed portion.

By using a sensitizer together with the photopolymerization initiator, the sensitivity can be improved and the wavelength range effective for the reaction can be extended. Specific examples of the sensitizer include 2,4-dimethylthioxanthone, 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-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4-dimethylaminobenzal) acetone, 1,3- Carbonyl bis (4-diethylaminobenzal) acetone, 3,3-carbonylbis (7-diethylaminocoumarin), triethanolamine, methyldiethanolamine, triisopropanolamine, N-phenyl-N
-Ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, benzoic acid (2-dimethylamino ) Ethyl, (n-butoxy) ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, 1-phenyl-5-ethoxycarbonylthiotetrazole and the like. . 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 of the sensitizer is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 10 parts by weight, based on the amount of the photosensitive organic component. By setting the amount of the sensitizer to be in this range, good photosensitivity can be obtained while maintaining the residual ratio of the exposed portion. In the present invention, an antioxidant is preferably added. The antioxidant has a radical chain inhibiting action, a triplet eliminating action, and a hydroperoxide decomposing action. When the photosensitive paste is used, for example, for manufacturing a partition wall of a member for a plasma display, light scattering of exposure light is inevitable due to the inclusion of many inorganic fine particles. Filling (residual film formation) is likely to occur. 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 the resin is cured at a low exposure dose due to light scattering, it is dissolved in the developing solution, the thickening of the pattern shape and the filling between the patterns are eliminated, and the resolution range is wide even if the exposure dose is increased. When an antioxidant is added to the photosensitive paste, the antioxidant captures radicals and returns the energy state of the excited photopolymerization initiator and sensitizer to the ground state, thereby generating extra light due to scattered light. The reaction is suppressed, and a photoreaction occurs abruptly at an exposure dose that cannot be suppressed by the antioxidant, so that 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 oxa Rate, phenyl-β-naphthylamine, parabenzylaminophenol, di-β-naphthylparaphenylenediamine, dinitrobenzene, trinitrobenzene, picric acid, quinonedioxime, cyclohexanone oxime, pyrogallol, tannic acid, triethylamine hydrochloride, dimethylaniline hydrochloride Salt, cuperon, (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-tert-butyl-4-hydroxyphenyl) propionate], 1,2,3-triene Hydroxybenzene, 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 to be added is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight in the photosensitive paste. By keeping the addition amount of the antioxidant within this range, it is possible to maintain the photosensitivity of the photosensitive paste, maintain the degree of polymerization and maintain the pattern shape, and increase the contrast between dissolution and insolubility in the developer. Can be.

By adding an ultraviolet absorber, scattered light inside the paste due to exposure light can be absorbed and scattered light can be reduced. Examples of the ultraviolet absorber include a benzophenone-based compound, a cyanoacrylate-based compound, a salicylic acid-based compound, a benzotriazole-based compound, an indole-based compound, and inorganic fine metal oxides.
Of these, benzophenone-based compounds, cyanoacrylate-based compounds, benzotriazole-based compounds, and indole-based compounds are particularly effective. Specific examples of these include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,
2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2 '
-Carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2
-Hydroxy-4-n-octoxybenzophenone, 2
-Hydroxy-4-octadecyloxybenzophenone,
2,2 ′, 4,4′-tetrahydroxybenzophenone,
4-dodecyloxy-2-hydroxybenzophenone, 2
-Hydroxy-4- (2-hydroxy-3-methacryloxy) propoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole,
-(2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-
3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′,
5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-4'-n-octoxyphenyl) benzotriazole, 2-ethylhexyl-2-cyano-3,3-diphenyl Acrylate, 2
-Ethyl-2-cyano-3,3-diphenyl acrylate, BONASORB U which is an indole-based absorbent
A-3901 (manufactured by Orient Chemical Co., Ltd.), BONASOR
B UA-3902 (manufactured by Orient Chemical Co.) SOM-2
-0008 (manufactured by Orient Chemical Co., Ltd.) and the like, but are not limited thereto. Further, a methacryl group or the like may be introduced into the skeleton of these ultraviolet absorbers and used as a reaction type. In the present invention, one or more of these can be used. The amount of the ultraviolet absorber added is preferably 0.001 to 10 parts by weight in the paste, more preferably 0.001 to 10 parts by weight.
It is in the range of 5 to 5 parts by weight. By setting it within this range, the transmission limit wavelength and the wavelength gradient width can be kept within desired ranges, and the effect of absorbing scattered light can be obtained while maintaining the transmittance of exposure light and the sensitivity of the photosensitive paste.

In the present invention, an organic dye can be added as a mark for exposure and development. By adding a dye and coloring, visibility is improved, and it becomes easy to distinguish a portion where the paste remains and a portion where the paste has been removed during development. The organic dye is not particularly limited, but preferably does not remain in the insulating film after firing. Specifically, azo dyes, anthraquinone dyes, indigoid dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes Dyes, phthalimide dyes, perinone dyes and the like can be used. In particular, it is preferable to select a material that absorbs light having wavelengths near the h-line and the i-line, for example, a carbonium-based dye such as basic blue, because the effects of the present invention can be more easily achieved. The added amount of the organic dye is preferably 0.001 to 1% by weight.

An organic solvent is used to adjust the viscosity when applying the photosensitive paste to the substrate according to the application method. 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, bromobenzene, Chlorobenzene, dibromobenzene, dichlorobenzene,
Bromobenzoic acid, chlorobenzoic acid, and the like, and an organic solvent mixture containing at least one of them are used.

The photosensitive paste is usually composed of inorganic fine particles and a reactive polymer, a reactive monomer, a reactive oligomer, an ultraviolet absorber, an antioxidant, an organic dye, a dispersant, a light absorber,
And a photosensitive organic component composed of a solvent and the like 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 photosensitive paste is adjusted to about 2000 to 200,000 cps (centipoise) with an organic solvent before use. For example, when the coating on the substrate is performed by spin coating,
000 cps is preferred. 50,000 to 200,000 cp to obtain a film thickness of 10 to 20 μm by applying once by screen printing
s is preferred. When using a blade coater method, a die coater method, or the like, 10,000 to 50,000 cps is preferable. As the organic solvent used at this time, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone,
Examples thereof include cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, and an organic solvent mixture containing at least one of these. Filler B
When the dispersion solvent of the oxide fine particles is different from the solvent of the photosensitive organic component, aggregation of the filler B can be avoided by mixing and using these solvents.

Hereinafter, a method for producing the photosensitive paste of the present invention will be described, but the present invention is not limited thereto. A step of removing all or a part of chlorine ions from the photosensitive organic component by an ion exchange method is used. As an example of ion exchange, there is a method of mixing and stirring at least a photosensitive organic component and a granular ion exchange resin, and then removing the ion exchange resin by filtration or the like. In this case, 40-7
When heated to 0 ° C., the viscosity of the photosensitive paste decreases, so that the efficiency of ion exchange increases and the operability of filtration improves. The anion exchange resin is based on a copolymer of a monovinyl aromatic compound such as styrene, vinyltoluene, and ethylstyrene and a polyvinyl compound such as divinylbenzene, trivinylbenzene, divinyltoluene, and divinylxylene. After reacting with a haloalkylating agent such as methyl methyl ether, chloroethyl methyl ether, chloromethyl ethyl ether, bromomethyl methyl ether, bromoethyl methyl ether, or bromomethyl ethyl ether to perform haloalkylation, dimethylamine, trimethylamine, triethylamine, etc. Those obtained by reacting with an amine to introduce an anion exchange group having a primary to tertiary amino group and / or a quaternary ammonium group can be used. Here, an example of an ion exchange method using an anion exchange resin is shown, but the present invention is not limited to these individual methods, and anion exchange membranes, anion exchange fibers, hydrated bismuth oxide, lead hydroxide phosphate, etc. By using the inorganic anion exchanger of the above, chloride ions can be adsorbed or ion-exchanged from the photosensitive organic component, and the amount thereof can be reduced. Further, the method for producing a photosensitive paste of the present invention may include a step of removing all or a part of chloride ions from the photosensitive organic component by an ion exchange method, or a step of simultaneously removing cations. preferable. That is, the cation exchange is performed after or simultaneously with the anion exchange to reduce the cations, thereby improving the dispersibility of the filler. Cation exchange is specifically performed by using an ion exchange resin having a cation exchange group such as a sulfonic acid group or a carboxylic acid group, a cation exchange membrane, a cation exchange fiber or an inorganic cation exchanger. Ions can be adsorbed or ion-exchanged to reduce the amount.

There is also a method in which the above-described anion exchange resin is mixed with a mixture of the photosensitive organic component and the filler B, stirred, and then the ion exchange resin is removed by filtration or the like.
Thereby, all or a part of the chlorine ions contained in the filler B can be removed. Also in this case 40-7
When heated to 0 ° C., the viscosity of the photosensitive paste decreases, so that the efficiency of ion exchange increases and the operability of filtration tends to improve. Filler B has an average particle size of 0.003
０．０0.02 μm, which is very small compared to the particle size of the ion exchange resin, so that it is not removed during filtration and is contained in the organic component. Although an example of the ion exchange method using an ion exchange resin is shown here, the present invention is not limited to these individual methods, and any ion exchange method can be used.
Further, the present invention may include a step of removing all or a part of chloride ions from the photosensitive paste containing the photosensitive organic component and the filler B by an ion exchange method, or a step of simultaneously removing cations. preferable. That is, cation exchange is performed after or simultaneously with anion exchange to reduce cations, so that dispersibility can be further improved.

Hereinafter, an example of a method for manufacturing a display member using a photosensitive paste will be described, but the present invention is not limited to this.

An address electrode is formed on a substrate by using a conductive metal. Silver, copper, chromium, aluminum, nickel, gold, or the like can be used as the conductive metal.
The address electrodes are formed in a stripe shape having a width of 20 to 100 μm. Next, it is preferable to form a dielectric layer so as to cover the electrodes.

Next, the photosensitive paste is applied entirely or partially on the dielectric layer or the substrate on which the electrodes are formed. As a coating method, a method such as a screen printing method, a bar coater, a roll coater, a die coater, or a blade coater can be used. The coating thickness can be adjusted by selecting the number of coatings, the screen mesh, and 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, 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.

After application, exposure is performed using an exposure apparatus. 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.

After the exposure, development is carried out using the difference in solubility between the exposed portion and the unexposed portion in the developing solution. In this case, the development is performed by an immersion method, a spray method, or a brush method. The developing solution used for the developing treatment preferably contains water as a main component. An organic solvent in which an organic component in the photosensitive paste can be dissolved can be used for the developer. In addition, water may be added to the organic solvent as long as its solubility is not lost. 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, 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, 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 good. 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
It is preferable to perform calcination by holding at a temperature of 10 ° C. for 10 to 60 minutes.

[0055]

EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. The specific method of the measuring method described in the examples is as shown below. (Measurement method) (1) Measurement of average particle size of filler B added to photosensitive paste Microtrac particle size analyzer UPA150MODEL
No. 9340 (Nikkiso Co., Ltd.). (2) Measurement of chlorine ion concentration in photosensitive paste A 2-inch silicon wafer is precisely weighed, and the photosensitive paste is applied thereon by a spinner. Dry at 80 ° C. for 30 minutes with a hot air dryer. The weight after drying is precisely weighed, and the weight of the nonvolatile component in the photosensitive paste is determined from the difference in weight.
A photosensitive paste is applied on a 2-inch silicon wafer with a spinner under the same conditions as above. After drying at 80 ° C. for 30 minutes using a hot air drier, the coating film is dissolved in a 0.5% aqueous NaOH solution, and the amount of chlorine ions is measured by an ion chromatography method.
The measured value is shown in an amount based on the weight of the nonvolatile component. (3) Measurement of electric conductivity Electric conductivity meter model CM-3 manufactured by Toa Denpa Kogyo Co., Ltd.
It was measured at 25.0 ° C. using 0S.

Example 1 γ-butyrolactone 26.3
Then, 17.5 g of the photosensitive polymer was mixed with the resulting mixture and heated to 60 ° C. with stirring to dissolve all the polymers. Photopolymers include Cyclomer P (Daicel Chemical Products AC
A320, molecular weight 28,000, acid value 120). Add a photosensitive monomer (M
GP400) 7.5 g, photopolymerization initiator (IC-369)
After adding 2.5 g and a sensitizer (2,4-diethylthioxanthone) 2.5 g, the photosensitive organic component was dissolved by stirring with an ultrasonic stirrer for about 30 minutes to form a uniform solution. 12.6 g of a weak anion exchange resin was added to the mixture, and the mixture was stirred at 45 ° C. and 60 rpm, filtered under pressure through a 400-mesh filter, and 56.0 g of a low-melting glass treated with an azo organic dye and 7 A of filler A were added. 2.0 g and 7.0 g of the filler B, and 125 rpm using three rollers.
m. As an ion exchange resin, a weak anion exchange resin “Amberlyst” A-21 (having a tertiary amino group and a partly quaternary ammonium group (OH type) ion exchange group) manufactured by Organo Corporation is used as γ-butyrolactone. It was used after washing. The low-melting glass has an oxide-converted composition of 6.7% by weight of lithium oxide, 22% by weight of silicon oxide, 32% by weight of boron oxide, 3.9% by weight of barium oxide, 19% by weight of aluminum oxide, and 2. 2% by weight, magnesium oxide 5.5% by weight, calcium oxide 4.1% by weight, glass transition point 497 ° C, softening point under load 530 ° C,
The coefficient of thermal expansion was 75 × 10 ⁻⁷ / K and the refractive index was 1.58. The glass component is made into fine powder with an attractor in advance,
It was a non-spherical powder having an average particle size of 2.6 μm. To 56.0 g of this glass powder, 0.045 g of the azo organic dye Sudan IV was dissolved in acetone, a dispersing agent was added, and the mixture was stirred homogeneously with a homogenizer. After dispersion and mixing, acetone was evaporated using a rotary evaporator and dried at a temperature of 150 ° C. Filler A has an oxide equivalent composition of 38% by weight of silicon oxide, 10% by weight of boron oxide, 5% by weight of barium oxide, and 36% by weight of aluminum oxide in terms of an analysis value.
Calcium oxide 5%, magnesium oxide 6% by weight, glass transition point 625 ° C, softening point under load 750 ° C,
The refractive index was 1.59. As the filler B, a 20% concentration solution in which titanium oxide having an average particle diameter of 0.005 μm (5 nm) was dispersed in γ-butyrolactone in a nearly monodispersed state was used.

The photosensitive paste thus obtained had a chlorine ion content of 490 ppm. Electric conductivity is 140 ×
It was 10 ^-4 S / m.

Using the photosensitive paste, a partition was prepared. 500 address electrodes having a line width of 40 μm and a pitch of 150 μm were formed on a glass substrate (PD200 manufactured by Asahi Glass Co., Ltd.) by a photolithography method using a photosensitive silver paste.

Next, a glass paste consisting of 50% by weight of glass powder, 15% by weight of titanium oxide, 20% by weight of ethylcellulose and 15% by weight of a solvent was applied on the electrode by screen printing, and then fired at 550 ° C. to obtain a dielectric material. A layer was formed.

On the dielectric layer, apply a photosensitive paste of 125 m
It was applied on a m-square glass substrate by screen printing using a 325 mesh screen. Coating and drying were repeated several times to avoid pinholes and the like in the coating film, and the film thickness was adjusted. Drying on the way is 10 at 80 ° C.
Minutes. Then, it was kept at 80 ° C. for 1 hour and dried. A coating film having a thickness of 200 μm after drying was formed.

Subsequently, a pitch of 150 μm and a line width of 50 μm
20mW / from the top using a negative chrome mask
Proximity exposure was performed using an ultra-high pressure mercury lamp with a cm ² output.
The exposure amount was 600 mJ / cm ² .

Next, a 0.2% aqueous solution of monoethanolamine kept at 35 ° C. is developed by applying a shower for 300 seconds, and then washed with water using a shower spray to remove a space portion that has not been photocured. Thus, a stripe-shaped partition pattern was formed on the glass substrate.

The partition pattern thus obtained was fired in air at 600 ° C. for 15 minutes to form a partition. When the cross-sectional shape of the formed partition wall was observed with an electron microscope, it was a rectangle having a height of 150 μm, a line width of 60 μm at the center of the partition wall, and a pitch of 150 μm.

Comparative Example 1 A photosensitive paste was obtained in the same manner as in Example 1 except that no ion exchange resin was used. The chlorine ion concentration in this photosensitive paste was 510 ppm. The electric conductivity was 160 × 10 ⁻⁴ S / m.
Using the photosensitive paste, a partition was produced in the same manner as in Example 1. Observation of the cross-sectional shape of the formed partition wall with an electron microscope showed a height of 150 μm and a line width of 1 at the center of the partition wall.
00 μm, line width at the bottom of partition wall 50 μm, pitch 150 μm
Indicates a pattern characteristic in which the central portion of the partition wall is thick.

Example 2 The composition was the same as that of Example 1 except that the filler B was 7.0 g and the photosensitive organic component was 56.3.
5.6 g of a weak anion exchange resin "Amberlyst" A-21 was added to a mixture consisting of
After stirring for 16 hours, the mixture was filtered under pressure with a 400 mesh filter to remove the ion exchange resin. To this, 56.0 g of low melting glass and 7.0 g of filler A were added, and 3
Using this roller, kneading was performed at 125 rpm. The chlorine ion concentration in this photosensitive paste was 300 ppm. The electric conductivity was 80 × 10 ⁻⁴ S / m. A partition was produced in the same manner as in Example 1. When the cross-sectional shape of the formed partition wall was observed with an electron microscope, the height was 150 μm,
It was a rectangle having a line width of 65 μm and a pitch of 150 μm at the center of the partition wall.

Comparative Example 2 Photosensitization was performed in the same manner as in Example 2 except that the cation exchange resin "Amberlyst" 15-E manufactured by Organo Co., Ltd. was used instead of the weak anion exchange resin of Example 2. A paste was obtained. The chlorine ion concentration in this photosensitive paste was 520 ppm. The electric conductivity was 170 × 10 ⁻⁴ S / m. Using the photosensitive paste, a partition was produced in the same manner as in Example 1. When the cross-sectional shape of the formed partition wall was observed with an electron microscope, it was found that the center of the partition wall was thick with a height of 150 μm, a line width of 90 μm at the center of the partition, a line width of 40 μm at the bottom of the partition, and a pitch of 150 μm.

From Examples 1 and 2 and Comparative Examples 1 and 2, dispersion of the filler in the photosensitive paste was stabilized by reducing chloride ions in the photosensitive paste, and a good partition wall shape was obtained. I understood.

(Example 3) Except that 5.6 g each of the weak anion exchange resin "Amberlyst" A-21 and the cation exchange resin "Amberlyst" 15-E manufactured by Organo Co., Ltd. were used in Example 1, In the same manner as in Example 1, a photosensitive paste was obtained. The chlorine ion concentration in this photosensitive paste is 80 pp
m. The electric conductivity was 60 × 10 ⁻⁴ S / m. Using the photosensitive paste, a partition was produced in the same manner as in Example 1. When the cross-sectional shape of the formed partition wall was observed with an electron microscope, it was a rectangle having a height of 150 μm, a line width of 55 μm at the center of the partition wall, and a pitch of 150 μm.

In Example 3, the electric conductivity was reduced by removing anions and cations at the same time, and a more favorable pattern could be formed.

From Examples 1 to 3 and Comparative Examples 1 and 2, it was found that by reducing the electric conductivity in the photosensitive paste, the dispersion of the filler was stabilized and a good partition shape was obtained.

[0071]

According to the photosensitive paste of the present invention, the dispersion of the filler contained in the photosensitive paste can be stabilized. A display member having a partition formed by favorable patterning using a photosensitive paste by photolithography and having excellent display characteristics such as chromaticity, luminance, and contrast can be obtained.

Continued on the front page F term (reference) 2H025 AA02 AA03 AA11 AB20 AC01 AD01 BC31 BJ00 CB43 CC08 CC20 FA29 2H089 HA36 QA16 5C027 AA09 5C040 GF18

Claims (8)

[Claims] 1. A photosensitive paste containing inorganic fine particles and a photosensitive organic component, wherein an electric conductivity at 25 ° C. is in a range of 0.1 to 150 × 10 ⁻⁴ S / m. Photosensitive paste. 2. A photosensitive paste containing inorganic fine particles and a photosensitive organic component, wherein the concentration of chlorine ions in the photosensitive paste is in the range of 0.001 to 500 ppm. 3. The method according to claim 1, wherein the inorganic fine particles have a low melting point glass powder of 50 to 50%.
90 parts by weight, filler A having an average particle size of 1.5 to 4 μm
Is from 0 to 30 parts by weight and the average particle size is from 0.003 to 0.
3. The photosensitive paste according to claim 1, wherein the filler B has a thickness of 3 to 50 parts by weight. 4. The photosensitive paste according to claim 3, wherein the filler A is at least one selected from cordierite and high melting point glass powder. 5. The photosensitive paste according to claim 3, wherein the filler B is at least one selected from the group consisting of alumina, zirconia, titania, ceria, yttria, tin oxide and silica. 6. The photosensitive paste according to claim 3, wherein the low melting point glass powder has the following composition in terms of oxide. Lithium oxide, sodium oxide or potassium oxide 3 to 15 parts by weight Silicon oxide 5 to 30 parts by weight Boron oxide 20 to 45 parts by weight Barium oxide or strontium oxide 2 to 15 parts by weight Aluminum oxide 10 to 25 parts by weight Magnesium oxide or calcium oxide 2 ~ 15 parts by weight 7. The method according to claim 1, wherein the photosensitive organic component contains a polymer having a carboxyl group in a side chain.
3. The photosensitive paste according to item 1. 8. A member for a display, wherein a partition is formed by using the photosensitive paste according to claim 1.