JP2000075502A - Developing method of inorganic fine particle-containing photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a developing method reduced in the cost required for waste liquid disposal concerned with a spent developer produced at the time of high pressure spray-developing an inorganic fine particle-containing photosensitive resin composition, secured in the safety of water environment and solved about the restriction by water environmental law. SOLUTION: The developing method is constituted so as to separate solid matter from the spent developer produced by high pressure spray-developing the inorganic fine particle-containing photosensitive resin composition and to reutilize the spent developer for the high pressure spray development of the inorganic fine particle-containing photosensitive resin composition. In such a case, the inorganic fine particle-containing photosensitive resin composition is a partition forming composition containing at least an inorganic fine particle, a photosensitive agent and a photosetting agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for developing a photosensitive composition in a microlithography process for forming a fine pattern. In particular, the present invention relates to a method for reducing an environmental load by reusing a used developer in a step of developing a photosensitive resin composition containing inorganic fine particles in forming a structural pattern such as a partition wall of an element for a plasma display.

[0002]

2. Description of the Related Art In recent years, in the field of displays and circuit materials, it has become increasingly necessary to process inorganic materials with high precision. For example, in order to form a wall partition which is a partition of each pixel of the plasma display panel, an inorganic material such as glass is processed into a pattern with high accuracy and a high aspect ratio, and the partition is formed by the pattern.

[0003] In order to form a pattern of this kind of inorganic material, a coating layer of a photosensitive composition containing inorganic fine particles, an organic binder, a sensitizing agent and the like is provided, and a pattern-like exposure is performed on the coating layer. A method of forming a pattern-like structure by dissolving the coating layer with water or an alkaline developer and dissolving and removing the soluble portion after a difference in solubility is caused between the and the non-exposed portion. Is adopted.
In the formation of plasma display panel walls and pattern processing of other dielectric layers and insulator layers, the thickness of the photosensitive composition layer is large because the pattern thickness needs to be increased, and the developing action does not reach deep parts. However, there are disadvantages such as the legs of the pattern remaining without being dissolved, and conversely, the upper layer of the pattern being subjected to excessive dissolution. In order to solve the problem, a method is effective in which water or an alkaline aqueous solution is jetted into the photosensitive composition layer in the form of a high-pressure jet to remove the uncured portion by both a dissolving action and a physical pressurizing action. In the following description of this specification, this developing method is referred to as high pressure spray development. Further, the developer used for high-pressure spray development of the inorganic fine particle-containing photosensitive composition is water or an alkaline aqueous solution, but the `` developer '' in the following description includes water in the case of water development. I have.

[0004] Incidentally, such a used developer for high-pressure spray development contains the components of the non-pattern portion of the photosensitive composition in a dissolved state or a solid dispersed state.
That is, the dissolved components include linear polymers (organic binders), unreacted monomers, dyes and other functional compounds. Many of the lysed components are non-biodegradable or hardly biodegradable and are unsuitable for microbial treatment. The inorganic fine particles are glass powder, alumina powder,
Pigments, phosphor particles, and the like, and particularly often contain low melting point lead glass. Therefore, this used developer is an industrial waste as generally called development wastewater or development wastewater.
It cannot discharge into public sewage.

[0005] Disposal of a used developer which cannot be discharged into the sewage or the natural environment can be entrusted to an industrial waste disposal company if the amount is small. Since the development processing operation is substantially the injection of a large amount of water (or an aqueous alkaline solution), the amount of the development waste liquid is large, and if the disposal is entrusted, the disposal cost becomes extremely high and the economical cost is increased. Does not hold. Therefore, there is a need for an economically feasible waste liquid disposal method for spent developer in high pressure spray development. Conventionally, in the field of microelectronics using a photosensitive composition such as a photoresist, high-pressure spray development that generates a large amount of used developer has not been performed, and therefore, the amount of wastewater is relatively small, and the treatment is as follows. And entrusted disposal to an industrial waste disposal contractor. However, the used developer for high-pressure spray development is not practically entrusted to disposal, and has not been purified by electrodialysis because the dissolved component contains many nonionic components.

[0006]

The object of the present invention is to provide a developing method which solves the above-mentioned problems relating to a used developing solution generated when a photosensitive resin composition containing inorganic fine particles is subjected to high-pressure spray development. is there. More specifically,
It is an object of the present invention to provide a developing method in which the waste liquid disposal cost relating to the used developer for the high-pressure spray development is reduced, the safety of the water environment is ensured, and the restrictions of the water environment regulations are solved.

[0007]

In order to solve the above-mentioned problems, the present inventor has studied a method of reducing the amount of used developer discharged to the level of the amount of waste liquid for developing a photoresist as a solution. It has been found that the used developer for high-pressure spray development can still be used as developing water despite the quality of the water that cannot be discharged according to both the general wastewater standard and local environmental regulations. As a result of repeated studies based on this discovery, the present inventors have reached the present invention. That is,
The present invention has the following configurations.

[0008] 1. After the solid content is separated from a used developer obtained by high-pressure spray development of the inorganic fine particle-containing photosensitive resin composition, the used developer is subjected to high-pressure spray development of a new inorganic fine particle-containing photosensitive resin composition. A method for developing a photosensitive resin composition containing inorganic fine particles, wherein the photosensitive resin composition is reused.

[0009] 2. 2. The developing method according to item 1, wherein the photosensitive resin composition containing inorganic fine particles is a composition for forming a partition wall containing at least inorganic fine particles, a photosensitive agent and a photocuring agent.

[0010] 3. (1) The applied pressure of high-pressure spray development is at least 50 kgf / cm ^2.
Or the development processing method according to 2.

4. 4. The method for treating a developer according to any one of the above items 1 to 3, wherein a solid content is settled and separated from the used developer, and the supernatant is further filtered (filtered) or dialyzed.

5. At least 30 VO of used developer
5. The developing method according to any one of the above items 1 to 4, wherein 1% is reused.

6. 6. The developing method according to any one of the above items 1 to 5, wherein the inorganic fine particles contain at least one of a glass powder and an alumina powder.

7. 7. The developing method according to any one of the above items 1 to 6, wherein the inorganic fine particle-containing photosensitive resin composition is a photosensitive resin composition used for forming a pattern of an element for a plasma display or a plasma addressed liquid crystal display. .

The present invention has been achieved based on the following three findings. That is, (1) The increase in the dissolved concentration of lead in the developer due to the repeated use of the developer almost reaches a peak at about 11 mg / liter (based on lead). The solubility product of lead hydroxide (Pb (OH) ₂ ) is 1.1 × 10 ^{-20 in} Chemical Handbook. If this solubility is followed, the concentration of lead should be about 1 × 10 ⁻⁷ mol / l in an almost neutral developer having a pH of about 6 to 7, which is lower than the environmental regulation value of each region. Become. But,
The concentration of lead dissolved in the used high-pressure spray developer is much higher than this value and exceeds environmental standards and local environmental regulations. It is presumed that the reason for the dissolution exceeding the solubility product is probably the dissolution in the form of lead acid ions or lead oxide. When the used developer is repeatedly used for the development of the inorganic fine particle-containing photosensitive composition, the concentration of the dissolved lead further increases. However, it was found by actual measurement that when the lead concentration increased to approximately 11 mg / liter, the developer was used repeatedly for repeated development, and the lead concentration did not increase any more.

(2) Dissolved lead does not affect development characteristics. It was confirmed that high-pressure spray development using a developer containing the highest concentration of lead of the used high-pressure spray developer of 11 mg / liter had no effect on pattern formability.

(3) The components of the photosensitive composition containing inorganic fine particles do not affect the developing characteristics. When high-pressure spray development is performed, organic components such as a binder polymer that have not been photocured in the composition dissolve in the used developer. The amount is about 0.5 g / L per one development, and naturally the concentration increases with each reuse, and the viscosity of the developer tends to increase. However, it was found that the presence of about 3 g / L of the organic component did not affect the efficiency of high-pressure spray development.

The present invention has been made based on the above three findings. In the development processing method of the present invention based on the above facts, a very simple operation of removing an insoluble residue mainly composed of inorganic fine particles from a used developing solution, the used developing is carried out by the following inorganic fine particle photosensitive composition. It is used again for developing the product. As a result, the amount of the used developer liquid entrusted to disposal can be minimized.

It is known in silver halide photosensitive materials that a new chemical is added to a developing waste solution and returned to the composition of the replenisher and reused, but in the present invention,
The technical issues that make reuse possible are concerns about a decrease in development efficiency due to an increase in the viscosity of the developer and concerns about a deterioration in pattern forming ability due to the inclusion of lead. In contrast to the case of use, the operation for reuse in connection therewith is also different in terms of technical concept and operation, such that no chemical operation is required in the present invention. Further, the basic technical field to which the present invention belongs is the photoresist field, and in this field, the development waste liquid is such that the dissolved organic components including the binder polymer increase in viscosity with time and lose fluidity, and Since the solubility of the developer changes to affect the profile of the pattern formed, the idea of reusing the developer could not be considered.

That is, although the present invention is a method which enables reuse of a developer by a simple operation, it is a method realized based on the above-mentioned technical study, and is a method which is realized in the field of a silver halide photosensitive material. Reuse is foreign and the re-use of processing solutions is not conceivable in the photoresist art, and is not implied by either.

It should be noted that the meaning of the terms "disposal" and "treatment", which are used in connection with the development waste liquid and the like in this specification, are as follows: the former is based on the Waste Cleaning Law (the law on the disposal and cleaning of waste). )) Is synonymous with "disposal", and means the safe disposal of waste as required by law, and "treatment" means the operation of adding waste to that purpose.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION (Development processing step) The developer used in the development processing method of the present invention includes water, an aqueous solution of amines such as tetramethylammonium hydroxide aqueous solution and monomethanolamine, alkali hydroxide and alkali carbonate. , And water is particularly preferred. In areas where the hardness of the water is high, the water for the developing solution is preferably deionized water which has been treated with an ion exchange resin or the like to remove the contained metal salts. Further, a water softener represented by ethylenediaminetetraacetic acid, nitrilotriacetic acid, or an alkali metal salt or an ammonium salt thereof may be added.

The used developer is allowed to stand still to allow solids to sediment spontaneously or to be separated by centrifugal sedimentation.
The solid is inorganic fine particles such as glass powder and alumina particles of the inorganic photosensitive composition component. The solids settle relatively easily and in a short period of time from the developer left standing even during spontaneous settling. After settling, the supernatant is separated from the precipitate by decantation.

When the amount of used developer is large and spontaneous sedimentation by standing is not appropriate, centrifugation is preferred, and continuous centrifugation by a rotary cylindrical device is particularly preferred. The used developer is continuously supplied to a portion near the rotation axis of the rotating cylindrical portion, and the inorganic fine particles move to the circumferential portion due to a difference in density with an aqueous medium (developer) and acceleration due to centrifugal force. In addition, since a sieve for filtration is provided in the circumferential portion in a cylindrical shape, the inorganic fine particles do not pass through the sieve, and only the filtrate is taken out from the outer edge of the cylindrical portion. Sedimentation is easy due to the high density of the microparticles, and any centrifuge can be selected. As a preferred example of the continuous centrifuge, a sludge isolator manufactured by Asahi Sunac Co., Ltd. is suitable, but of course, the centrifuge used in the present invention is not limited to this.

The used developer from which solids have been separated can be further filtered or dialyzed to remove fine insolubles that have not settled and separated, thereby increasing the ratio of reused solution in the developer. it can. For this purpose, it is particularly preferred that the developer is filtered using any known sand filtration device. If the filter layer of sand is clogged with continuous use, the blocking material can be removed by back washing and the filter bed can be reused. These details are described in an appropriate reference book (for example, p. 203 of Irrigation Wastewater Handbook published by Maruzen Co., Ltd. 1990).

Appropriate filtration means other than sand filtration may be used. For example, a qualitative filter paper of the second type defined by Japanese Industrial Standards (JIS P3801, filter paper) or a filter paper having a finer filter material structure than that (for example, third, fourth and 5B to 5C) can be preferably used. Further, a cylindrical core filter made of expanded polyethylene or expanded polystyrene used in a processing liquid circulation system of an automatic developing machine for a silver salt photosensitive material may be diverted. In this case, a filter having a pore size of 25 microns has a transmission speed and a collection efficiency. It is preferable in satisfying both.

In addition, cellulose or a cellulose derivative may be precoated on a filtration layer of an arbitrary filtration device and filtered. These cellulosic precoat materials are:
When the binder of the photosensitive composition containing inorganic fine particles contains the above-described cellulose derivative, it is particularly effective in that the ratio of the reused solution in the developer can be increased.

Dialysis may be performed instead of filtration. For dialysis, a synthetic membrane of cellophane or other regenerated cellulose, collodion, polyacrylonitrile, ethylene / vinyl alcohol copolymer, polysulfone, or the like is preferable. A membrane having a tubular structure having a high area density, such as a cellophane tube, may be used, or a dialysis membrane in which an alumite or iron mesh plate is used as a support plate for a filter medium may be used.

The used developer from which the solids have been separated is used as at least a part of a developer for developing the following photosensitive composition containing inorganic fine particles. At the time of reuse, the used developer from which solids have been separated may be used as it is without being mixed with a newly prepared developer, but preferably, the used developer is used in an amount of 30 vol% or more of the whole. Preferably at least 50 vol%, particularly preferably 70 vol%
It is preferable to use it by mixing it with a newly prepared developer so that the concentration becomes 1% or more. The upper limit of the mixing ratio is determined as a range that does not cause a reduction in the development efficiency of high-pressure spray development or a decrease in the quality of a formed pattern that occurs when only the used developer is repeatedly used and reused. Of 90
If it is at most vol%, such a problem will not occur. If the number of repetitive development operations is three or less, the development can be continued without any problem even if the next developer is composed only of the used developer without mixing with the newly prepared development. In this method, the amount of the waste developing solution other than the solid matter to be disposed of on a consignment basis is, for example, 14 to 18 vol% of the amount of the developing waste solution when not reused when the ratio of the reused developing solution in the developer is 80 vol%. Become.

(High-Pressure Spray Development) Next, the high-pressure spray development according to the present invention will be described. The high-pressure spray development is a development method in which a developing solution is sprayed in a fine powder form onto a surface of a photosensitive composition coating layer by a high-pressure injection device to perform development. When the developing solution is jetted at a high pressure, the developing action extends to the deep part, and the non-cured part, that is, the non-pattern part is effectively dissolved, flows out into the liquid, and the insoluble inorganic fine particles in that part can also be removed.

The injection angle of pressurized injection of water or an alkaline aqueous solution has a great effect on the developing action. The developing action is strongest when it is perpendicular to the surface of the photosensitive composition. On the other hand, removal of inorganic fine particles derived from the partition wall material for plasma display is not sufficient simply by a strong developing action, and unnecessary inorganic fine particles must be removed from the substrate by mechanical impact of a developer. For this purpose, it is preferable that the fuel is injected at an angle of obliquely forward or obliquely backward from the vertical direction by 0 to 35 degrees, preferably 0 to 20 degrees. The applied pressure for injecting water or an alkaline aqueous solution varies depending on the shape of the injection nozzle. Cat Eye Nozzle (Cross Section Lens Shape) as a Preferred Embodiment of the Present Invention
In the case of 50 to 350 kgf / cm ² , preferably 10
A pressure of 0-300 kgf / cm ² is effective.

It is practical to employ a continuous development step as an economical embodiment of the present invention. In this case, the fan or the aqueous alkaline solution should be spread evenly in the width direction of the composition layer. A method in which injection nozzles that eject with a mold spread are arranged individually or in plurals in the spreading direction of a fan, and the photosensitive composition passes through a spray portion of water or an alkaline aqueous solution while conveying the photosensitive composition at a constant speed in a direction perpendicular to the fan surface. Therefore, it is preferable to carry out the development processing continuously. The injection liquid amount is 0.5 to 20 liters / minute, preferably 1 to 15 liters / minute per injection nozzle.

In this developing method, since the developing action extends to the deep part, it is possible to increase the height of the partition walls, and it is also possible to use large inorganic particles which are generally difficult to remove. Therefore, in the method of the present invention, the thickness of the photosensitive composition can be as high as 15 to 300 microns, preferably 50 to 200 microns. In particular, when a partition having a high wall is formed, the thickness can be increased by overlapping coating. High-pressure injection can effectively develop even a partition having a height of 300 microns.

A developing apparatus suitable for carrying out the present invention having the above-described injection pressure, impact angle, and water flow spreading shape is an ultra-high pressure jet precision cleaning system AF series (Asahi Sunac Corporation). Among them, AF5400S is for high pressure,
AF2800II is suitable for low pressure. However, the device is not limited to this type as long as it has the above-described injection pressure, impact angle, and water flow spreading shape.

A preferred photosensitive resin composition containing inorganic fine particles for use in these display elements is a photosensitive resin composition containing the above-mentioned inorganic fine particles, a polymer binder, a photosensitive agent, a photocuring agent and a hydrolyzable polymerizable organometallic compound. And further preferably contains a monomer containing an epoxy group.

[Photosensitive Composition Containing Inorganic Fine Particles] The composition of the photosensitive composition containing inorganic fine particles which is the object of the present invention is as follows:
50 to 95% by weight, preferably 70 to 95% by weight of inorganic fine particles and 5 to 50% by weight, preferably 5 to 30% by weight
Consisting of organic components. When the amount of the organic component is small, the shrinkage ratio during firing is small and the shape change due to firing is small, which is preferable. The organic component includes a binder component, a photosensitive agent, a photocuring agent, a hydrolyzable organic metal compound, and the like. As the binder component, a water-soluble group-substituted cellulose derivative described later is preferable.

(Inorganic Fine Particles) The inorganic fine particles are not particularly limited as long as they are generally used in this technical field, and the method of the present invention can be applied. Examples thereof include glass, ceramics (alumina, cordierite, etc.), and metal. (Gold, platinum,
Particles such as silver, copper, nickel, palladium, tungsten, ruthenium oxide and their alloys), metal oxides of the above metals, oxides of rare earth elements, and phosphors, which are composite compounds of these oxides, are commonly used. Can be Among them, glass and ceramics containing silicon oxide, boron oxide or aluminum oxide as an essential component are often used. These are insulators and are used for forming insulating patterns, particularly for forming partitions of plasma displays and plasma addressed liquid crystal displays.

The particle size of the inorganic fine particles is selected in consideration of the shape of the pattern to be produced. The higher the height of the partition walls, the finer the particles are desired. Usually, the average particle diameter is 20 μm or less, particularly 0.01 to 10 μm.

As a composition in the glass fine particles, silicon oxide is blended in a range of 3 to 80% by weight, and in most cases, 20 to 60% by weight. Among them, bismuth oxide,
Contains any one of the lead oxides and has a content of 5
６０60% by weight of low melting glass fine particles, or a total of 8 to 60% by weight of boron oxide, bismuth oxide or lead oxide, and at least one of lithium oxide, sodium oxide and potassium oxide Of glass particles containing 3 to 15% by weight.

Various metal oxides may be added as inorganic fine particles. The pattern after firing can be colored by adding the metal oxide. For example, a black pattern can be formed by including 1 to 10% by weight of a black metal oxide in the photosensitive composition. Oxides of Cr, Fe, Co, Mn, Cu, and Ru are selected as black or other colored metal oxides used for this purpose. By containing 10% by weight, a black pattern with higher light opacity can be formed. Although not a coloring material, fine particles of alumina are also used as a material for forming the partition walls.

Further, by using a composition to which an inorganic pigment that develops a color such as red, blue, or green in addition to black is added,
A pattern of each color can be formed. These coloring patterns can be suitably used for a color filter of a plasma display and the like. The inorganic fine particles account for at least 60% by weight, preferably 70 to 95% of the solid component of the photosensitive composition.
% By weight.

(Binder Component) As the binder,
Known binder components such as polyvinyl alcohol, polyvinyl butyral, methacrylate polymer, acrylate polymer, poly (butyl methacrylate) resin, α-styrene polymer, and α-methylstyrene polymer are used, and other water-soluble group-substituted celluloses Derivatives are particularly preferred binders for the photosensitive composition for forming barrier ribs.

The water-soluble group-substituted cellulose derivative may contain at least one of a lower alkyl group and a lower acyl group as a substituent in addition to the water-soluble group. Further, after the substitution with the water-soluble group and the lower alkyl group or the lower acyl group, a urethane acrylate may be further added to the hydroxyl group of the glucose chain. Examples of the water-soluble substituent include a hydroxyalkyl group having 1 to 4 carbon atoms, a carboxyalkyl group having 1 to 4 carbon atoms, and a phthalic acid group which may be substituted with a lower alkyl group and may be hydrogenated. And phosphate groups. Particularly, a hydroxyalkyl group and a carboxyalkyl group are preferred. The lower alkyl group or acyl group which may be contained in addition to the water-soluble substituent is an alkyl group having 1 to 3 carbon atoms, an acetyl group, a formyl group and a succinyl group.

Incidentally, as a general form of a cellulose derivative generally called hydroxyalkylcellulose,
A hydroxypolyalkoxyalkyl group formed by further ether-bonding the hydroxyalkyl group to the hydroxyalkyl group of the cellulose derivative substituted with these hydroxyalkyl groups may be used. Preferred examples of the hydroxyalkyl-substituted cellulose derivative include a cellulose derivative substituted with a hydroxyethyl group, a hydroxyethoxyethyl group, a hydroxyethoxyethoxyethyl group, and the like, and a hydroxypropyl group, a hydroxypropoxypropyl group, a hydroxypropoxypropoxypropyl group, and the like. Also included are cellulose derivatives which have been prepared.

Particularly preferred cellulose derivatives are hydroxypropylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, carboxyethylcellulose, hydroxypropylmethylcellulose, hydroxymethylphthalate cellulose, hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose acetate phthalate and cellulose sulfate. is there.

In the present invention, a monomer multi-substituted cellulose derivative to which a monofunctional or polyfunctional polymerizable monomer is added may be used. Particularly preferred polymerizable functional group-containing cellulose derivatives include the above-mentioned hydroxyalkyl cellulose or hydroxyalkyl.
It is a polymer monomer obtained by adding urethane acrylate to an alkyl co-substituted cellulose derivative. Specific examples thereof include a cellulose derivative to which a reaction product of 2,4-tolylene diisocyanate and 2-hydroxyethyl methacrylate has been added.

The preferred amount of the water-soluble group-substituted cellulose derivative in the composition is 2 to 50% by weight, more preferably 2 to 40% by weight of the total solid.

(Photosensitive Agent) The photosensitive agent in the present invention is a monomer having a photopolymerizable group, and may be monofunctional or polyfunctional. Here, as the photopolymerizable group, for example, an acryloyl group, a methacryloyl group, an acrylamide group,
Allyl group, vinyl ether group, vinyl thioether group,
Examples thereof include a vinylamino group, a glycidyl group, and an acetylenically unsaturated group.

Specific examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate,
Isopropyl acrylate, n-butyl acrylate,
sec-butyl acrylate, iso-butyl 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, isoproponyl acrylate, 2
-Hydroxypropyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, allyl 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, Pentaerythrito Monohydroxypentaacrylate, ditrimethylolpropane tetraacrylate, glycerol diacrylate, methoxylated cyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, triglycerol diacrylate, trimethylolpropane triacrylate, acrylamide, Aminoethyl acrylate and the like can be mentioned.

In addition, monomers containing an aromatic ring, for example, phenyl acrylate, phenoxyethyl acrylate, benzyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, bisphenol A diacrylate, and diacrylate bisphenol of bisphenol A-ethylene oxide adduct A-propylene oxide adduct diacrylate, thiophenol acrylate, benzyl mercaptan acrylate, a monomer in which 1 to 5 hydrogen atoms of these aromatic rings are substituted with chlorine or bromine atoms, or styrene, p-methyl Styrene, o-methylstyrene, m-methylstyrene, chlorinated styrene, brominated styrene, α-
Methylstyrene, chlorinated α-methylstyrene, brominated α
-Methyl styrene, chloromethyl styrene, hydroxymethyl styrene, carboxymethyl styrene, vinyl naphthalene, vinyl anthracene, vinyl carbazole and the above compounds in which some or all of the acrylates in the molecule have been changed to methacrylates, γ-methacryloxypropyl triacrylate Examples include methoxysilane and 1-vinyl-2-pyrrolidone. In the present invention, one or more of these can be used.

N, N'-methylenebisacrylamide, hexamethylenebisacrylamide, unsaturated acid amide obtained by condensing a polyamine compound with an unsaturated acid, unsaturated amide having a hydroxyl group, for example, N-methylolacrylamide Unsaturated acid amides such as unsaturated amide compounds obtained by reacting the compound with a polycarboxylic acid, a polyepoxy or the like are also used.

These photosensitizers can be prepared by adding a photoreactive group to a side chain or a molecular terminal to a polymer described above as a binder or a polymer or oligomer obtained by polymerizing the above photosensitizer. Also, a photosensitive polymer or a photosensitive oligomer having the above structure can be used. Preferred photoreactive groups are those having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acryl group, and a methacryl group.

The method of adding such a side chain to an oligomer or a polymer is based on an ethylenically unsaturated compound having a glycidyl group or an isocyanate group or an acrylic acid with respect to a mercapto group, an amino group, a hydroxyl group or a carboxyl group in the polymer. There is a method in which chloride, methacrylic chloride or allyl chloride is added to make an addition reaction. Examples of the ethylenically unsaturated compound having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, glycidyl ether crotonic acid, glycidyl ether isocrotonic acid, and the like. Examples of the ethylenically unsaturated compound having an isocyanate group include (meth) acryloyl isocyanate,
(Meth) acryloylethyl isocyanate and the like.
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.

The amount of the photosensitive agent to be added is 10 to 200 parts by weight, preferably 50 to 150 parts by weight, based on the binder. If the amount is less than 10 parts by weight, the curing speed is not sufficient.
On the other hand, when the amount exceeds 200 parts by weight, it becomes difficult to fire at the time of forming the partition walls, which is not preferable.

(Photocuring Agent) The photosensitive composition containing inorganic fine particles, which is the object of the present invention, usually contains at least one of a photocuring agent, ie, a photoradical generator, a photoacid generator and a photobase generator. Contains.

Examples of the photo radical generator include DB
E [CAS No. 10287-53-3], benzoin methyl ether, anisyl (p, p'-dimethoxybenzyl), TAZ-110 (trade name, manufactured by Midori Kagaku Co., Ltd.), benzophenone, TAZ-111 (trade name: manufactured by Midori Kagaku Co., Ltd.) ), IR-651 and 369 (trade name: Ciba-Geigy).

Examples of the photoacid generator include a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, and a known photoacid used in a micro resist. , A compound capable of generating an acid and a mixture thereof can be appropriately selected and used.

Among them, the following compounds are used. (A) An oxazole derivative or s-triazine derivative substituted with a trihalomethyl group. For example, 2-trichloromethyl-5- (4-chlorobenzylidenemethyl) oxadiazole, 2,4,6-trichloromethyltriazine and the like. (B) an iodonium salt or a sulfonium salt bonded to two or three aryl groups. For example, bis- (4,4′-trifluoromethylphenyl) iodonium, trifluoromethylsulfonate and the like. (C) Disulfone derivatives or iminosulfonate derivatives. For example, bis (4-chlorophenylsulfone), 1,3-dioxo-2- (4-methoxyphenylsulfoxy) -4,5-benzopyrrol and the like. (D) inter alia, benzoin tosylate, α-methylbenzoin tosylate, pyrogallol trimesylate, D
NB-101 (trade name: manufactured by Midori Kagaku Co., Ltd.), NB
-101 (trade name: manufactured by Midori Kagaku Co., Ltd.), NB-2
01 (trade name: manufactured by Midori Kagaku Co., Ltd.).

Examples of the photobasic generator include NBC
-101 (trade name: manufactured by Midori Kagaku Co., Ltd.), α, α-
Dimethyl-3,5-dimethoxybenzyl carbamate and the like can be mentioned.

Examples of those having both properties of a photo radical generator and a photo acid generator include TAZ-113 (trade name: manufactured by Midori Kagaku Co., Ltd.) and TPS-105 (trade name: manufactured by Midori Kagaku Co., Ltd.) ), BBI-101 (trade name: manufactured by Midori Kagaku Co., Ltd.), BBI-105 (trade name: manufactured by Midori Kagaku Co., Ltd.), DPI-105 (trade name: manufactured by Midori Kagaku Co., Ltd.), and the like.

The content of the photocuring agent is usually in the range of 0.001 to 40% by weight, preferably 0.05 to 20% by weight, more preferably 0.1 to 10% by weight of the amount of the photosensitizer. . The addition amount is appropriately selected depending on the properties of the organic phase and the inorganic phase.
It is 1 to 20 parts by weight, preferably 0.2 to 15 parts by weight, more preferably 0.5 to 12 parts by weight.

(Hydrolysable organometallic compound) The photosensitive composition containing inorganic fine particles may contain a hydrolyzable organometallic compound. Here, the hydrolyzable organometallic compound means a hydrolyzable polymerizable compound represented by the following general formula (1). (R ¹ ) _n -X- (OR ² ) _4-n (1) In the general formula (1), R ¹ and R ² may be the same or different and represent an alkyl group or an aryl group. , X
Represents Si, Al, Ti or Zr, and represents an integer of 0 to 2. When R ¹ or R ² represents an alkyl group, it preferably has 1 to 4 carbon atoms. Further, the alkyl group or the aryl group may have a substituent. This compound is a low molecular compound and preferably has a molecular weight of 1,000 or less.

The compound containing aluminum in the hydrolyzable polymerizable compound includes, for example, trimethoxyaluminate, triethoxyaluminate, tripropoxyaluminate and tetraethoxyaluminate. Examples of those containing titanium include, for example, trimethoxy titanate, tetramethoxy titanate, triethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, chlorotrimethoxy titanate,
Examples thereof include chlorotriethoxytitanate, ethyltrimethoxytitanate, methyltriethoxytitanate, and phenyltriethoxytitanate. As a material containing zirconium, for example, a zirconate corresponding to the material containing titanium can be given.

Examples of compounds containing silicon in the hydrolyzable polymerizable compound include, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, dimethyldiethoxysilane. Silane, phenyltrimethoxysilane, phenyltriethoxysilane,
Cyphenyldimethoxysilane, diphenyldiethoxysilane, and the like can be given.

The compound of the formula (1) may be partially hydrolyzed and then dehydrated and condensed. In addition, a trialkylmonoalkoxysilane can be added as needed to adjust the physical properties of the product. The hydrolysis-polymerizable organometallic compound is a compound constituting the inorganic phase in the photosensitive composition of the present invention. In order to enhance the storage stability of the inorganic phase, the hydrolysis-polymerizable organometallic compound is represented by the general formula (1). An active metal hydroxyl group, for example, a silanol group (Si-OH) of an inorganic polymer obtained by partially hydrolyzing and polymerizing a decomposition-polymerizable organometallic compound is converted to t.
-It is effective to protect by etherification (Si-OR) with a higher alcohol such as butanol and i-propyl alcohol.

It is considered that the hydrolyzable polymerizable compound described herein is mostly present in the developer residue in a form adsorbed on the surface of the inorganic fine particles. When the organic component is removed by heat treatment of the residue, the inorganic component such as silicon is incorporated into the inorganic fine particles in the form of an oxide.

The content of the hydrolysis-polymerizable organometallic compound in the photosensitive composition containing inorganic fine particles can be used in a wide range, and is usually 1 to 80% of the organic component, preferably 1 to 80%.
It is used in a range of 40%, more preferably 1 to 20%.

The above radical polymerizable compound is not an essential component of the organic / inorganic composite composition, but when it is added therein, its content is 10% of the amount of the hydrolyzable organometallic compound.
To 500%, preferably 30 to 400%.

[Preparation of Partition Pattern Structure] (Coating of Photosensitive Composition) The photosensitive composition containing inorganic fine particles of the present invention comprises a water-soluble group-substituted cellulose ester, a photosensitive agent,
The photocuring agent and the hydrolysis-polymerizable organometallic compound may be formed by uniformly mixing them, or may be formed by dissolving them in an appropriate solvent. In addition, a water-soluble group-substituted cellulose ester and a photosensitizer, and, if necessary, a photocuring agent are mixed in the presence or absence of a solvent and dissolved in a polar solvent to form an organic phase. According to the above, a radical polymerizable monomer may be mixed with an aqueous mixed solvent to form an inorganic phase, and the organic phase and the inorganic phase may be uniformly mixed to form the inorganic phase. Here, a photocuring agent can be added to the inorganic phase. Alternatively, the inorganic phase may be formed by uniformly mixing and dissolving the hydrolysis-polymerizable organometallic compound and the radical-polymerizable monomer, polymerizing to a predetermined degree of polymerization, and further uniformly dissolving the photocuring agent.

The viscosity of the photosensitive composition is appropriately adjusted by the addition ratio of inorganic fine particles, a thickener, an organic solvent, a plasticizer, a suspending agent, etc., but the range is 200,000 to 200,000.
It is cps (centipoise). For example, when coating on a glass substrate is performed by a spin coating method, 200 to 5000
cps is preferred. In order to obtain a film thickness of 10 to 20 μm by applying once by a screen printing method, 50,000 to 200,000 cps is preferable. When a blade coat method, a die coater method, or the like is used, 5000 to 100,000 cps is preferable.

When used for a partition for plasma display, various components such as inorganic fine particles, an ultraviolet light absorber, a photosensitive polymer, a photosensitive monomer, a photopolymerization initiator, a glass frit and a solvent usually have a predetermined composition. After mixing as described above, the mixture is homogeneously mixed and dispersed with a three-roller or a kneading machine to produce.

On a glass substrate, a ceramic substrate, or a polymer film, the above kneaded composition is applied over the entire surface or in the form of a photosensitive paste. As a coating method, a general method such as screen printing, a bar coater, a roll coater, a die coater, and a blade coater can be used. The coating thickness is
It can be adjusted by selecting the number of coatings, coater gap, screen mesh, and paste viscosity. There is a method of transferring a photosensitive paste layer provided on a polymer film to a glass substrate.

(Formation of Pattern Structure) After coating, exposure is performed using an exposure apparatus. The exposure is generally performed by a mask exposure using a photomask, as is performed by ordinary photolithography. As the mask to be used, either a negative type or a positive type is selected depending on the type of the photosensitive organic component. Also, without using a photomask, red or blue visible laser light, Ar ion laser, U
A direct drawing method using a V ion laser or the like may be used.

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

The active light source used at this time is, for example,
Visible light, near-ultraviolet light, ultraviolet light, electron beam, X-ray, laser light, etc. are preferable. Among them, ultraviolet light is preferable. Etc. can be used. Among these, an ultra-high pressure mercury lamp is preferred.
Exposure conditions vary depending on the coating thickness, but 1 to 100 mW / c
Exposure is performed for 0.1 to 30 minutes using an ultrahigh pressure mercury lamp having an output of m ² .

After the exposure, development is performed utilizing the difference in solubility between the photosensitive portion and the non-photosensitive portion in the developing solution. Water is usually used as a developer repeatedly used, but an alkaline aqueous solution may be used depending on the composition of the photosensitive composition. In each case, the development is by high-pressure spray development as described above. When the binder is the above-mentioned water-soluble group-substituted cellulose derivative, development with water is preferred. On the other hand, when a compound having an acidic group such as a carboxyl group is present in the photosensitive composition (for example, when the binder of the inorganic fine particles is carboxymethylcellulose), it may be preferable to develop with an aqueous alkali solution rather than with water. As the alkaline aqueous solution, a metal alkaline aqueous solution such as sodium hydroxide, sodium carbonate, or calcium hydroxide aqueous solution can be used, but in addition, an organic alkaline aqueous solution may be used.

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 alkaline aqueous solution is usually 0.01 to 10% by weight, more preferably 0.1 to 10% by weight.
~ 5% by weight. If the alkali concentration is too low, the soluble portion is not removed depending on the composition of the photosensitive composition, and if the alkali concentration is too high, the pattern portion may be peeled off and the non-soluble portion may be corroded, which is not preferable. The development temperature during development is preferably from 20 to 50 ° C. from the viewpoint of process control.

From the developer used for the development, the solids taken in during the development are separated and the liquid phase portion is left as it is, or after further filtration or dialysis, the reusable portion is at least 50 vol% or more. Thus, it is mixed with a fresh developing solution and used for the next developing process. The details are as described above.

The glass substrate having the partition layer obtained by the above steps can be used on the front side or the back side of the plasma display. Further, it can be used as a substrate for discharging an address portion of a plasma addressed liquid crystal display.

After the phosphor was applied between the formed partition layers, the glass substrates on the front and rear surfaces were sealed together, and helium,
By encapsulating rare gases such as neon and xenon,
A panel portion of a plasma display can be manufactured. Furthermore, by mounting a driver IC for driving,
A plasma display can be manufactured.

The embodiment of the present invention in which a developer is repeatedly used in high-pressure spray development of a photosensitive composition containing inorganic fine particles has been described above. However, the method of the present invention is not limited to application to plasma display panel production. It can be used in the field of microlithography for the purpose of improving discrimination between a pattern and a non-pattern portion.

[0082]

The present invention will be specifically described below with reference to examples. However, the present invention is not limited to this.

Example 1 (Preparation of photosensitive composition) After mixing the following organic components and inorganic components, 15 parts of an organic component, 85 parts of an inorganic component,
The following paste-form photosensitive composition was prepared by kneading 3 parts of glycerin with a mixed solvent of ethyl cellosolve / methanol (1/1).

Inorganic component Alumina powder (average size 0.1 micron) 15 parts Glass A (average size 1 micron) (see Table 2) 80 parts Surface-modified silica (average size 0.02 micron) 5 parts (3-methacrylic) Organic component Hydroxypropylcellulose (degree of substitution 3.0) 70 parts Polyethylene glycol methacrylate (oxyethylene chain 2-4) 30 parts 2,2-dimethoxy-1,2-diphenylmethane-1-one 3 copies

Next, on a 30 cm square soda glass substrate,
The composition was applied a plurality of times to a coating thickness of 150 μm, and then dried at 80 ° C. for 30 minutes.

(Pattern Exposure) Next, exposure was performed through a photomask. As the mask, a chrome negative mask having a pitch of 130 μm and a line width of 30 μm was used. Exposure is 5
Ultraviolet light exposure was performed with an ultrahigh pressure mercury lamp having an output of 0 mW / cm ² at a light amount of 50 mJ / cm ² .

(Development) In the development, an ultra-high pressure jet precision cleaning system AF5400S was used while the exposed photosensitive composition was conveyed on a sample stage at a constant speed of 5 mm / sec.
The spraying was performed by spraying a thin layer of water spray spreading in a fan shape onto the surface of the photosensitive composition using (Asahi Sunac Co., Ltd.). The water is sprayed at an angle such that the fan-shaped spray surface is perpendicular to the direction of travel of the composition and the spray is directed toward the direction of travel of the composition at an angle of 10 ° with respect to a plane perpendicular to the surface of the composition. Went in a relationship. In addition. Five spray nozzles are arranged so that the spray acts uniformly in the width direction of the composition surface. The injection pressure at that time was 200 kgf / c ² , and development was performed at an injection amount of 5 liters / minute with 5 nozzles for 5 minutes. The processing amount during this period was 300 g, expressed as the amount of the photosensitive composition processed. As a result of peeling off the formed partition wall pattern and measuring, it was found that the composition formed on the substrate as the partition wall was about 35%, and the remaining, that is, 65% was dissolved or dispersed in the used developer. Was.

Next, 50 liters of the used developing solution was centrifuged by a small continuous centrifugal separator (Sludge Isolator manufactured by Asahi Sunac Co., Ltd.).
Liter), take 10 liters of fresh water to make 50 liters, and use this as a developer.
The above development was repeated. This developing operation was repeated five times.

(Evaluation and Results) For each of the first to fifth developments, the lead concentration in the developer after development was determined by the atomic absorption method, and was derived from the composition which was dissolved in the developer and was not photocured. The amount of the dissolved organic component was measured by evaporation to dryness, and the profile of the obtained partition pattern was evaluated. The profile of the partition pattern was evaluated by cutting the partition pattern sample and observing the cross section with a scanning electron microscope.
The case where no good partition was formed due to lack of pattern, lack of disconnection, poor removal of unexposed portion, or dissolved organic component due to poor development (excessive local dissolution or insufficient dissolution), The case where the formation defect was mild was rated as Δ. Particularly excellent and particularly inferior partition patterns were indicated by ◎ and XX, respectively. In addition, if you add it just in case, quantification of lead concentration and measurement of dissolved organic components are
This was performed to obtain reference data, and the effect of the development processing method of the present invention is directly shown by the pattern profile. Table 1 shows the obtained results.

[0090]

[Table 1]

As can be seen from Table 1, although the lead concentration and the amount of dissolved organic components increased with the number of developments, the pattern profile showed little sign of deterioration. The amount of waste developer discharged during the five development operations was 3
It was 0 liter (assuming that 40 liters of the fifth used developer was reused), and 20 liters of a residue containing insoluble solids. If the conventional developing process without reusing the developing solution of the present invention is performed, the amount of the developing waste liquid in five times becomes 250 liters containing the solid content. The amount of waste that could not be discharged into the country was reduced to 1/5. In addition, the high-pressure spray developing device is
Until the second development, a normal discharge rate (10 l / min) was maintained under the specified applied pressure without any abnormality.

Example 2 The following organic component and inorganic component were mixed, and then kneaded with a mixed solvent of ethyl cellosolve / methanol (1/1) at a ratio of 15 parts of the organic component, 85 parts of the inorganic component, and 3 parts of glycerin to form a paste. Of the photosensitive composition. Inorganic component Alumina powder (average size 0.1 micron) 15 parts Glass A (average size 1 micron, see Table 2) 80 parts Surface modified silica (average size 5 microns) 5 parts (3-methacryloxypropyltrimethoxysilane) Modification) Organic component Hydroxypropyl cellulose (degree of substitution 4.0) 62 parts Hydroxyethyl cellulose / urethane acrylate adduct ¹⁾ 8 parts Polyethylene glycol methacrylate (oxyethylene chains 2 to 4) 30 parts 2,2-dimethoxy-1,2- Diphenylmethane-1-one 3 parts (Note) 1) Hydroxyethyl cellulose to which the reaction product of 2,4-tolylene diisocyanate and 2-hydroxyethyl methacrylate is added

The composition containing the glass fine particles A was applied in a plurality of times by screen application in the same manner as in the example.
Formation of a coating layer of 50 μm, drying at 80 ° C. for 30 minutes, and light intensity of 30 mJ / cm by an ultra-high pressure mercury lamp through a photomask
² was exposed to ultraviolet light. For each of them, development for 2 minutes at an injection speed of 10 liter / min was repeated 5 times by the same spray developing apparatus as in Example 1. The obtained pattern profile was good for any pattern using any glass sample without any sign of deterioration up to 5 times of development (evaluation ○).
Met. According to the development processing method of the present example, the amount of waste that had to be entrusted to each of the samples A to D could be reduced to 1/5.

Example 3 The following organic component and inorganic component were mixed respectively, and kneaded with a mixed solvent of ethyl cellosolve / methanol (1/1) at a ratio of 15 parts of the organic component, 85 parts of the inorganic component, and 3 parts of glycerin to form a paste. Of the photosensitive composition. Inorganic component Alumina powder (average size 0.1 micron) 15 parts Glass A (average size 1 micron, see Table 2) 80 parts Surface modified silica (average size 5 microns) 5 parts (3-methacryloxypropyltrimethoxysilane) Modification) Organic component Carboxymethylcellulose (degree of substitution 1.5, manufactured by Shin-Etsu Chemical Co., Ltd.) 62 parts Hydroxyethyl cellulose / urethane acrylate adduct ¹⁾ 8 parts Polyethylene glycol methacrylate (oxyethylene chains 2 to 4) 30 parts 2 , 2-Dimethoxy-1,2-diphenylmethane-1-one 3 parts (Note) 1) Hydroxyethyl cellulose to which the reaction product of 2,4-tolylene diisocyanate and 2-hydroxyethyl methacrylate is added

The composition containing the fine glass particles A was coated by a screen coating method in the same manner as in Example 2 to form a coating layer having a thickness of 150 μm, dried at 80 ° C. for 30 minutes, and passed through a photomask. 30mJ / c
It was carried out ultraviolet exposure of m ^2. Using a 0.1% aqueous solution of monoethanolamine as a developing solution, development for 2 minutes at an ejection speed of 10 liter / min was repeated 5 times by the same spray developing apparatus as in Example 1. However, in this example, after insoluble solids were separated from the developing solution used for each development by natural sedimentation, 19 liters of the supernatant was used for Whatman No. 1 solution. The solution filtered using 1 filter paper was mixed with 1 liter of fresh developer and used for the next development.

The obtained pattern profiles from the first to fifth developments were all good (evaluation ○) without any sign of deterioration. The amount of waste was 5 liters containing an insoluble solid residue by this repetitive development method, and the amount of waste was 100 liters when the method of the present invention was not used.
I was able to lose more weight than liters.

Example 4 Preparation of Photosensitive Composition Containing Inorganic Fine Particles 4.0 g of tetraethoxysilane and 2.0 g of 3-acryloxypropylenetrimethoxysilane were put into a reactor, and 0.05N hydrochloric acid was added. The mixture was vigorously stirred for 30 minutes, and partially hydrolyzed and polymerized to obtain a homogeneous solution. 10 g of glass powder A shown in Table 2 was mixed with the mixture to obtain an inorganic component. In addition, 2.0 g of hydroxypropyl cellulose (degree of propylene oxide substitution per glucose unit: 4.
0, commercial product), 0.37 g of methylenebisacrylamide and 0.11 g of benzoin methyl ether
It was dissolved in 6.0 g of methyl cellosolve to obtain an organic component. The inorganic component and the organic component were mixed at a weight ratio of organic component / inorganic component of 25/75 to obtain a photosensitive composition containing inorganic fine particles.

Using this composition, a coating layer having a thickness of 150 μm was formed by multiple coatings by screen coating in the same manner as in Example 2, dried at 80 ° C. for 30 minutes, and illuminated with a super-high pressure mercury lamp through a photomask at a light intensity of 30 mJ /. Repeated high pressure spray development with water for 2 minutes at a jet rate of 10 liters / minute with UV exposure of cm ² . However, in this example, the number of repetitions was set to 10, and after insoluble solids were settled and separated from the developer for each development, filtration was performed using a commercially available sand filtration device, and then filtration was completed. The fresh solution 1 was mixed with the developing solution 4 at a volume ratio and used for the next development. The profile of each partition pattern from the first to the tenth time was all good. Further, the used developer which became excessive by mixing with the fresh liquid was stored as it was, used as the first backwash water at the time of backwashing of the sand filtration device, and then was disposed of on a consignment basis. By this method, the amount of waste was 30 liters of developing waste liquid and 10 liters of solid waste. Normal development without the method of the present invention produces 200 liters of waste liquid while reducing 20 wastes.
The amount could be reduced to vol%.

[0099]

[Table 2]

[0100]

According to the development processing of the present invention, a solid residue is separated from a used developer of a photosensitive composition containing inorganic fine particles, and the separated developer is mixed with at least 30 vol% of a fresh developer and reused. The method can greatly reduce the amount of development waste liquid and solid waste that require consignment disposal.

Claims (7)

[Claims] 1. A method for separating a solid content from a used developer produced by subjecting a photosensitive resin composition containing inorganic fine particles to high-pressure spray development, and then adding the used developer to a new photosensitive resin composition containing inorganic fine particles. A method for developing a photosensitive resin composition containing inorganic fine particles, wherein the photosensitive resin composition is reused for high-pressure spray development of a product. 2. The method according to claim 1, wherein the photosensitive resin composition containing inorganic fine particles is a composition for forming a partition wall containing at least inorganic fine particles, a photosensitive agent and a photo-curing agent. 3. The method according to claim 1, wherein the applied pressure of the high-pressure spray development is low.
Also 50kgf / cm ^Two2. The method according to claim 1, wherein
Or the development processing method according to 2. 4. The developing solution according to claim 1, wherein a solid content is separated by settling from the used developing solution, and the supernatant is further filtered (filtered) or dialyzed. Processing method. 5. The method according to claim 1, wherein at least 30 vol of the used developer is used.
The developing method according to any one of claims 1 to 4, wherein% is reused. 6. The developing method according to claim 1, wherein the inorganic fine particles include at least one of a glass powder and an alumina powder. 7. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition containing inorganic fine particles is a photosensitive resin composition used for forming a pattern of an element for a plasma display or a plasma addressed liquid crystal display. The development processing method described in 1. above.