JP2005322590A - Forming method of display device barrier rib and paint for display device barrier rib formation used for it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a forming method of display device barrier ribs with adhesiveness of photoresist improved and barrier rib forming efficiency by sandblast ameliorated and to provide paint used for it. <P>SOLUTION: In the method of forming the barrier ribs for the display device, in which, after a resist film of a required pattern is formed on a paint layer for forming barrier ribs having a given thickness placed on a substrate, unnecessary parts of the paint layer for forming the barrier ribs are removed by sandblast processing, the paint for forming the barrier ribs contains inorganic powder (A), an organic vehicle (B), and an Si-containing organic compound (C), and a content of the Si-containing organic compound (C) is 0.3 to 10 weight parts to 100 weight parts of the inorganic powder (A). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for forming a display device partition and a display device partition forming coating used therefor, and more specifically, the formation of a display device partition that improves adhesion with a photoresist and improves partition formation efficiency by sandblasting. The present invention relates to a method and a coating material for forming a display device partition used therein.

  In recent years, display devices such as plasma display panels (hereinafter referred to as PDPs) have attracted attention as large flat displays and have been realized and widely used as large television receivers. The PDP is an image in which a pair of glass plates are opposed to each other at a minute interval and discharged into a discharge space obtained by sealing the periphery, and a phosphor is stimulated to emit light by generated ultraviolet rays.

  A general AC type PDP has a structure as shown in FIG. Of the pair of glass plates, the glass plate on the side where an image is displayed on the PDP is called the front plate, and the other is called the back plate.

  The PDP front plate (10) is provided with a transparent electrode (11) formed of striped ITO or the like and a bus electrode (12) formed of one silver or the like provided on the transparent electrode. Yes. A transparent dielectric film made of glass or the like is formed so as to cover the bus electrode, and an MgO film (14) is formed by vapor deposition so as to cover the dielectric film.

  On the other hand, the PDP back plate has partition walls (16) arranged in parallel on the substrate (10) in stripes, and one address electrode is parallel to the partition walls (16) on the bottom surface of the recesses of the partition walls (16). An electrode (13), also called a dielectric layer (15), is formed, and a dielectric layer (15) is formed so as to cover the surface of the electrode (13). Furthermore, phosphors (17) indicated by R, B, and G, which are excited by ultraviolet rays, are applied to the wall surfaces of the partition walls (16).

  In this PDP back plate, first, a stripe-shaped electrode (13) is formed on a glass substrate (10) by patterning with a thick film material such as a silver paste, and then baked, and then on the electrode (13). A thick film material such as a dedicated glass paste to be used as the dielectric layer (15) is applied and baked. Finally, a partition wall-forming coating is applied on the dielectric layer (15), and the partition wall (16). It is manufactured by baking after patterning.

  In recent years, PDPs are required to have higher image quality, and in order to achieve this, the number of pixels is increased, and individual pixels have become finer. As the pixels become finer, it is required that the width of the partition wall, which has conventionally been 100 to 150 μm, and the interval which has been 300 μm be made finer and higher definition. The barrier ribs form a pattern by screen printing often used in thick film technology, but it is difficult to print a high-definition barrier rib pattern by screen printing. In addition, the height of the partition wall is usually 100 to 150 μm, but only 20 to 30 μm can be formed by one screen printing. Therefore, it is necessary to perform screen printing a plurality of times (repeatedly). However, it is difficult to repeatedly perform screen printing while forming a high-definition partition because accuracy cannot be ensured.

  From this point of view, after forming a photoresist layer on the substrate, exposing, developing, and forming a resin pattern with a photoresist on the substrate, using this resin pattern as a mold, filling the gap with a coating for forming a partition wall, A method of removing the resin pattern and baking it to form a partition wall has been studied.

  In this method, since the resin pattern is a mold, it is necessary to fill the partition wall forming paint in an amount sufficient to secure 100 to 150 μm as the height of the fired partition wall, and the resin pattern is a film of 200 to 300 μm. Requires thickness. Although an expensive photoresist is used as the material for the resin pattern, it is removed after filling with the partition wall forming paint and becomes useless in the subsequent process. Therefore, forming a resin pattern with a film thickness of 200 to 300 μm not only increases the price of the device, but also exposure of such a thickness is not preferable because the pattern accuracy is ensured.

  The resin pattern by the photoresist used as a mold has a larger area where the photoresist is in close contact as compared with a method of forming a partition by sandblast described later. This is because the interval is wide with respect to the width of the partition wall as described above. Therefore, in this method, the adhesion between the photoresist and the substrate is not a problem, but rather the step of removing the photoresist from the mold is a problem.

  That is, there is a problem that the pattern of the partition wall is destroyed when removing the resin (photoresist) of the mold. Therefore, a partition wall forming material containing a specific silane coupling agent has been proposed (see Patent Document 1). According to this method, since the partition wall forming material contains an isocyanurate-based silane coupling agent, the adhesion between the partition wall and the substrate is improved, and the photoresist removal process of the mold is improved, but only the resin pattern It is difficult to remove substantially.

  In order to cope with this, it has been studied that the partition walls are press-formed with a mold. A partition material for pressure formation that can form a high-definition partition wall by a simple process has been proposed (see Patent Document 2). This patent document intends to improve adhesion and alkali resistance after partition formation by adding a silane coupling agent to the partition wall-forming coating material (rib composition) and surface-treating the inorganic powder with modified silicone. It is a thing.

  However, this method has a problem in that the process for producing the partition wall-forming coating is complicated, and in particular, the inorganic powder surface-treated with such modified silicone is likely to aggregate, making it difficult to obtain a uniform partition-wall-forming coating. . The partition formation by pressure formation has a problem that the formed partition wall is easily deformed because there is no step of solidifying the partition wall forming paint such as drying.

By the way, sandblasting is frequently used in the partition forming step. This step is a step of removing unnecessary portions of the dried body of the partition wall forming material formed on one surface by sandblasting to form a partition pattern. A pattern in which a photoresist is exposed is disposed in a portion of the dry body that is desired to remain as a partition wall. A portion where the photoresist is disposed is not ground by sandblasting, and a dry body remains, thereby forming a partition pattern. After the barrier rib pattern is formed, the unnecessary photoresist is washed away with a stripping solution such as an alkaline aqueous solution such as Na ₂ CO ₃ .

  In this way, the photoresist patterning process forms a photoresist film on a dry body of the partition wall-forming coating material, irradiates ultraviolet rays through the mask on which the pattern is written, bakes the pattern, and irradiates ultraviolet rays with an alkaline aqueous solution. It is carried out through a development process for dissolving and removing the unsettled portion and a water washing process for washing with an alkaline aqueous solution.

In the patterning process with a series of these photoresists, it is necessary that the dry body of the partition wall-forming paint and the photoresist are in close contact, specifically, a dissolution process with an alkaline aqueous solution such as Na ₂ CO ₃ , It is required that a high-definition photoresist pattern is not washed away in the subsequent washing step.

  In addition, since the barrier rib pattern is formed by sandblasting using a photoresist, the width of the photoresist pattern is the width of the barrier rib. Therefore, in order to obtain a high-definition barrier with a width of 100 μm or less, a higher-definition photoresist is used. It is necessary to form a pattern. If the width of the photoresist pattern is narrowed, the area where the photoresist is in close contact with the dry body of the partition wall forming paint is reduced, and the adhesion is reduced accordingly. In order to increase the definition of the PDP, it is necessary to improve the adhesion between the photoresist and the partition wall forming coating material.

  By the way, in the dielectric layer and the partition including lead, not only when the PDP is discarded, but also in the partition forming process by sand blasting, the dry body of the partition forming paint ground by sand blasting is the earth as the waste containing lead. Will be released to the environment. In recent years, from such an environmental point of view, it has been studied to use glass containing no lead as an inorganic powder of a paint for forming a PDP dielectric layer and partition walls.

From such a viewpoint, a glass composition having a softening point of 600 ° C. or less and a specific thermal expansion coefficient and increasing the amount of B ₂ O ₃ has been proposed (see Patent Document 3). However, even if an attempt is made to prepare a partition wall-forming paint using such lead-free glass, it has been impossible to form partition walls by sandblasting for the reasons described later.
Japanese Patent Laid-Open No. 11-185643 JP 2000-268733 A JP-A-9-278482

  SUMMARY OF THE INVENTION In view of the above-mentioned problems of the prior art, the object of the present invention is to provide a method for forming a display device partition that can improve adhesion with a photoresist and improve partition formation efficiency by sandblasting, and a display device partition for use in the method. To provide paint.

  As a result of intensive research in order to solve such problems, the present inventors have found that a specific amount of the inorganic powder in the coating for forming a display device partition containing glass powder as an essential component of the inorganic powder. By blending the Si-containing organic compound, the inorganic powder is uniformly dispersed in the partition wall-forming coating material, and not only can the adhesion with the photoresist be improved, but also a high-definition photoresist pattern can be realized, At this time, if an inorganic powder having a specific amount of moisture adsorbed on the surface is used, the inorganic powder is formed in the partition wall-forming coating composition by hydrogen bonding between the OH group and the Si-containing organic compound caused by the water on the surface of the inorganic powder. It came to be uniformly dispersed, and it was found that a greater effect was obtained, and the present invention was completed.

  That is, according to the first invention of the present invention, a resist film having a desired pattern is formed on a partition wall-forming paint layer having a predetermined thickness installed on a substrate, and then the partition wall is formed by sandblasting. In the method for forming a partition wall of a display device by removing unnecessary portions of the coating layer for coating, the partition wall forming coating material includes an inorganic powder (A), an organic vehicle (B), and a Si-containing organic compound (C). And the content of Si containing organic compound (C) is 0.3-10 weight part with respect to 100 weight part of inorganic powder (A), The formation method of the display device partition characterized by the above-mentioned is provided.

According to a second aspect of the present invention, in the first aspect, the glass powder is SiO ₂ —B ₂ O ₃ —ZnO—alkaline glass containing no lead. A forming method is provided.

  According to the third invention of the present invention, in the first invention, the organic vehicle (B) comprises at least one resin selected from ethyl cellulose, nitrocellulose, acrylic, styrene, or butyral, terpinol, dihydrotel A display device partition wall comprising at least one solvent selected from pinol, butyl carbitol acetate, butyl carbitol, or 2,2,4-trimethyl-1,3-pentanediol monobutyrate A forming method is provided.

  Furthermore, according to the fourth invention of the present invention, in the first invention, the Si-containing organic compound (C) is a silane or silazane having a molecular weight (Mw) of 500 or less. A forming method is provided.

  On the other hand, according to the fifth invention of the present invention, it relates to the method of any one of the first to fourth inventions, comprising inorganic powder (A), organic vehicle (B) and Si-containing organic compound (C), And the content of Si containing organic compound (C) is 0.3-10 weight part with respect to 100 weight part of inorganic powder (A), The coating material for display device partition formation characterized by the above-mentioned is provided.

  According to the display device partition wall forming method of the present invention, since a paint containing a specific amount of an Si-containing organic compound is used, the dry body obtained by applying the paint has improved adhesion to the photoresist, and sandblasting. A fine photoresist pattern can be realized. Thereby, the width of the partition wall of the PDP can be reduced and a high-definition PDP can be realized.

  Further, even when a glass powder not containing lead is used as the partition wall forming coating material, the dried body is in close contact with the photoresist, and a fine photoresist pattern can be realized. As a result, a PDP partition wall having a resist line width of 100 μm or less that does not contain lead, which has been impossible until now, can be formed, and the industrial value is extremely high.

  Hereinafter, the coating material for forming a display device partition wall of the present invention (hereinafter also simply referred to as a coating material) and a method for forming a partition wall using the same will be described in detail.

  The coating material for forming a display device partition according to the present invention contains an inorganic powder (A), an organic vehicle (B), and a specific amount of an Si-containing organic compound (C). It is in a uniformly dispersed state.

1. Inorganic powder (A)
In the present invention, the inorganic powder is a main component of the coating material for forming the display device partition wall, and is a component that forms the partition wall by baking and simultaneously adheres the formed partition wall to the substrate. The inorganic powder has a function as a pigment for realizing a PDP partition wall of a desired color and a function as an aggregate of the PDP partition wall.

The inorganic powder includes, for example, glass powder having a softening point of 500 to 600 ° C. as an essential component. As the glass powder, not only PbO—SiO ₂ —B ₂ O ₃ glass containing lead but also SiO ₂ —B ₂ O ₃ —ZnO—alkali glass not containing lead can be used. The glass powder is selected depending on the desired softening point and whether the thermal expansion coefficient after firing the inorganic powder is compatible with the substrate.

The composition of the glass powder containing lead is not particularly limited, but PbO: 5 to 70% by weight, B ₂ O ₃ : 1 to 20% by weight, SiO ₂ : 5 to 60% by weight in terms of oxides. Al ₂ O ₃ : 15 wt% or less, ZnO: 20 wt% or less, BaO + CaO: 10 wt% or less, K ₂ O + Na ₂ O: 10 wt% or less are preferable.

If the composition of the glass powder is within this range, the thermal expansion coefficient of the glass powder is 80 × 10 ⁻⁷ or less, which is the same as or smaller than that of a soda lime glass substrate widely used for PDP. Shows excellent matching with the substrate. It is widely known that the thermal expansion coefficient of the soda lime glass substrate is 80 × 10 ^{−7 to} 86 × 10 ⁻⁷ . If the thermal expansion coefficient of the glass powder is extremely different from the thermal expansion coefficient of the substrate, the substrate, the dielectric film, and the PDP partition wall may be warped or distorted, leading to defects such as collapse of the PDP partition wall.

If the glass powder containing no lead in the present invention, the composition of the glass powder, in terms of oxide _B 2 _O 3: _{5~30 wt%,} SiO 2: 10 to 60 _wt%, Al ₂ O 3: 10 wt % or less, ZnO: 10 to 30 wt%, BaO + CaO: 10 wt% or _{less, K 2 O + Na 2 O} + Li 2 O: it is desirable that the 20 wt% or less.

  The glass powder preferably has a maximum particle size of less than 30 μm. When the maximum particle size of the glass powder exceeds 30 μm, a partition having a flat surface cannot be formed. It is desirable that the glass powder has a particle size distribution D50 value of 2.0 to 6.0 μm. When it is finer than 2.0 μm, it becomes difficult to control the firing temperature, and when it is higher than the predetermined temperature, the PDP partition wall may collapse. On the other hand, when the particle diameter is larger than 6.0 μm, it may be impossible to form a dense PDP partition wall.

  The content of the glass powder is preferably 70 to 99% by weight, particularly 80 to 90% by weight, based on the inorganic powder. When the content of the glass powder is less than 70% by weight, other inorganic powders are relatively increased and a dense partition cannot be realized. On the other hand, when the glass powder is more than 99% by weight, a dense partition can be formed, but since there are few other inorganic powders, a PDP partition of a desired color may not be realized. Moreover, when the content of the glass powder is more than 95% by weight, there are too few inorganic powders functioning as aggregates, and the PDP partition wall may melt and flow and collapse during firing.

  The inorganic powder contains, in addition to the glass powder, any inorganic oxide powder such as alumina, silica, forsterite, zirconia, zircon, and titania. Silica includes quartz glass in addition to α-quartz.

  As for the particle size of these inorganic oxides, the maximum particle size is desirably less than 30 μm. If the maximum particle size of the glass powder exceeds 30 μm, it is not preferable because a partition having a flat surface cannot be formed.

The composition ratio of the glass powder and the inorganic oxide powder is selected on the basis that a dense fired film can be obtained. The inorganic oxide powder must be smaller than the glass powder, and is desirably 1 to 30% by weight, preferably 5 to 20% by weight, based on the whole inorganic powder.
When the content is less than 1% by weight, not only a PDP partition wall of a desired color may not be realized, but the function as an aggregate is too weak, and the PDP partition wall may melt and flow and collapse during firing. is there. On the other hand, if it exceeds 30% by weight, a dense partition may not be realized.

  The inorganic powder used in the present invention contains water, but its content must be 0.1 to 1% by weight. The Si-containing organic compound is hydrolyzed by the water adsorbed on the surface of the inorganic powder, and hydrogen bonds with the inorganic powder. Since water is present on the surface of the inorganic powder, the Si-containing organic compound is selectively bonded to the inorganic powder. If the water content is less than 0.1% by weight, the hydrogen bonds are insufficient, while if it exceeds 1% by weight, the inorganic powder aggregates.

  Special conditions are not required for adsorbing a predetermined amount of water on the surface of the inorganic powder, but it should be stored in an environment where the temperature is 18 ° C to 27 ° C and the relative humidity is 40% to 60%. Is preferred. If the temperature is lower than 18 ° C. or the relative humidity exceeds 60%, the water content is more likely to exceed 1% by weight. On the other hand, if the temperature exceeds 27 ° C. or the relative humidity is less than 40%, the water content is likely to be less than 0.1% by weight.

2. Organic vehicle (B)
In the present invention, the organic vehicle contains an organic resin and a solvent, and has a function of dispersing inorganic powder in the paint and a function of bonding a partition formed by baking the paint to the substrate.

  The organic resin functions to maintain the strength of the dried body of the partition wall-forming coating, and in particular, prevents the partition wall pattern from collapsing after sandblasting and before firing. It is not desirable for the organic resin to remain on the partition after firing, and it is necessary to use an organic resin that decomposes at a firing temperature of 500 to 600 ° C.

  As such an organic resin, a resin such as ethyl cellulose, nitrocellulose, acrylic, styrene, or butyral can be used. These resins can be used alone or in combination of two or more. Acrylic includes a methacrylate resin, and styrene includes a methylstyrene resin.

  On the other hand, the solvent is a component that improves the fluidity of the paint. For example, terpinol, dihydroterpinol, butyl carbitol acetate, butyl carbitol, 2,2,4-trimethyl-1,3-pentanediol monobutyrate is selected. These solvents can be used alone or as a mixture.

3. Si-containing organic compound In the present invention, the Si-containing organic compound has a function of improving the adhesion between the inorganic powder in the dry body of the partition wall forming material and the organic resin and the photoresist in the dry body. A compound having —H bond, Si—O bond or Si—C bond.

  The Si-containing organic compound is not particularly limited as long as it has the above function. For example, halogenated silanes such as vinyltrichlorosilane (Mw = 161.5); vinyltrimethoxysilane (Mw = 148.2), vinyltriethoxysilane (Mw = 190.3), tetramethoxysilane (Mw = 152. 2), tetraethoxysilane (Mw = 208.3), methyltrimethoxysilane (Mw = 136.2), methyltriethoxysilane (Mw = 178.3), dimethyldiethoxysilane (Mw = 148.3), Phenyltriethoxysilane (Mw = 240.4), hexyltrimethoxysilane (Mw = 206.4), decyltrimethoxysilane (Mw = 262.5), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (Mw = 246.3), 3-glycidoxypropylmethyldiethoxysilane (Mw 248.4), 3-glycidoxypropyltriethoxysilane (Mw = 278.4), various alkoxysilanes such as p-styryltrimethoxysilane (Mw = 224.3); 3-methacryloxypropylmethyldimethoxysilane ( Mw = 232.4), 3-methacryloxypropyltrimethoxysilane (Mw = 248.4), 3-methacryloxypropylmethyldiethoxysilane (Mw = 260.4), 3-methacryloxypropyltriethoxysilane (Mw) = 290.4), (meth) acryl group-containing silanes such as 3-acryloxypropyltrimethoxysilane (Mw = 234.3); N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane (Mw = 206. 4), N-2 (aminoethyl) 3-aminopropyltrimethoxysilane (Mw = 222.4), N-2 (aminoethyl) 3-aminopropyltriethoxysilane (Mw = 264.5), 3-aminopropyltriethoxysilane (Mw = 179.3), etc. Silane; silazane such as hexamethyldisilazane (Mw = 161.4).

  These Si-containing organic compounds are desirably decomposed at a temperature (500 to 600 ° C.) at which the partition wall-forming coating material is fired and do not remain in the fired partition walls. Therefore, the molecular weight (Mw) is preferably 500 or less, particularly 400 or less, and further preferably 300 or less. Those having a molecular weight (Mw) exceeding 500 are not preferable because they are hardly decomposed by firing and remain in the fired partition walls.

  By the way, it is generally known that when an inorganic material such as ceramics or glass is surface-treated using a Si-containing organic compound, the adhesion between the inorganic material and an organic material such as a resin is improved. Conventionally, the surface treatment includes a method of adding the inorganic substance to an aqueous solution containing an Si-containing organic compound, stirring and wet-treating the surface, and a method of performing a surface treatment by spraying an aqueous solution containing an Si-containing organic compound onto the inorganic substance. There is.

  However, in any method, when the inorganic powder of the partition wall forming coating is surface-treated using an aqueous solution containing an Si-containing organic compound, the surface-treated powder is strongly aggregated. The inorganic powder thus formed cannot be dispersed in the resin or organic solvent of the partition wall-forming coating material, and a uniform coating material cannot be obtained. If a uniform partition wall forming coating material is not used, the partition wall firing process may lead to problems such as collapse of the partition wall due to material non-uniformity and peeling due to abnormal expansion.

Further, in the aqueous solution containing the Si-containing organic compound, the B ₂ O ₃ component in the glass powder out of the inorganic powder constituting the partition wall-forming coating material is eluted, so that the glass powder is altered, and the desired softening point and heat It becomes difficult to realize the expansion coefficient.

  The Si-containing organic compound is generally low in stability, and when it comes into contact with water, the functional group can be easily removed and easily hydrolyzed as described above, and the generated —OH group may be condensed to form an oligomer. The viscosity of paints containing Si-containing organic compounds is not stable over time, making them unsuitable for storage.

  On the other hand, in this invention, although inorganic powder contains water, the content is 0.1 to 1 weight%, and this water is adsorb | sucking to the surface of inorganic powder. The Si-containing organic compound is hydrolyzed by the water on the surface of the inorganic powder, and hydrogen bonds with the inorganic powder. Since water is present on the surface of the inorganic powder, the Si-containing organic compound is selectively bonded to the inorganic powder. If the water content is less than 0.1% by weight, the hydrogen bonds are insufficient, while if it exceeds 1% by weight, the inorganic powder aggregates.

  If the Si-containing organic compound is trialkoxysilane, it is hydrolyzed by water by the mechanism of the following formula, and OH groups generated by hydrolysis are hydrogen bonded to the surface of the inorganic powder, and the inorganic powder is formed by hydrogen bonding of the OH groups. It is thought that this will strengthen the bond.

(In the formula, R and R ′ are, for example, alkyl groups having 1 to 5 carbon atoms, and may be the same or different.)

Incidentally, was obtained using a barrier-forming coating material using glass containing lead, and only a paint forming a partition wall was replaced by SiO ₂ -B ₂ O ₃ -ZnO- alkali free glass above lead glass When the dried product is compared in the development process after the photoresist, the photoresist pattern remains in the development process with an alkaline aqueous solution and the water washing process in the partition wall forming coating using the glass powder containing lead, but the SiO ₂ —B _The partition wall-forming paint using ₂ O ₃ —ZnO-alkali glass powder does not remain at all. This indicates that the partition wall-forming paint using the SiO ₂ —B ₂ O ₃ —ZnO—alkali glass powder has low adhesion to the photoresist. Therefore, it is impossible to form a partition wall by sandblasting with a partition wall forming paint using glass powder containing no lead.

SiO ₂ —B ₂ O ₃ —ZnO—alkaline glass powder has low adhesion to the photoresist, which is due to the low water resistance of the glass. Since the glass is to achieve a desired softening point, the B ₂ O ₃ and alkali element, it contains more than glass containing lead. In particular, B ₂ O ₃ and alkali elements in glass are known to deteriorate the water resistance of glass. B ₂ O ₃ and alkali elements in the glass easily adsorb water. The photoresist that has been adhered to the dry body of the partition wall-forming coating by lamination is adsorbed by B ₂ O ₃ and alkali elements in the glass due to the aqueous alkali solution in the development process and the water in the water washing process. The photo resist is peeled off. This phenomenon is particularly noticeable in high-definition patterns.

Therefore, attempts have been made to refine the composition of SiO ₂ —B ₂ O ₃ —ZnO—alkaline glass and realize a desired softening point without containing B ₂ O ₃ more than necessary. However, even in this case, the water resistance of the glass does not reach the water resistance of the lead-containing glass, and the adhesiveness of the dry material for forming the partition wall to the photoresist is that using the glass containing lead. It is not enough. As a result, the partition wall-forming paint using glass containing no lead could not form the partition wall by sandblasting.

Further, as described above, when the inorganic powder is surface-treated with the aqueous solution of the Si-containing organic compound, B ₂ O ₃ in the glass constituting the inorganic powder is eluted into the aqueous solution, the glass is altered, and a desired softening point is obtained. May not be realized. This is remarkable in the SiO ₂ —B ₂ O ₃ —ZnO—alkaline glass containing no lead compared to the PbO—SiO ₂ —B ₂ O ₃ glass containing lead.

On the other hand, in the present invention, even when a SiO ₂ —B ₂ O ₃ —ZnO—alkali glass that does not contain lead is used, a specific amount of an Si-containing organic compound is contained as a component of the partition wall forming paint. Therefore, the adhesion between the dried body and the photoresist can be improved. The effect of the Si-containing organic compound is as described above, and improves the adhesion between the inorganic powder of the partition wall-forming paint, the resin and the photoresist. Further, the surface of the inorganic powder is covered with an Si-containing organic compound, and the glass in the inorganic powder makes it difficult to adsorb water in the photoresist development process and the water washing process.

4). Preparation Method of Partition Wall Forming Coating Material The partition wall forming coating material of the present invention is prepared by mixing an inorganic powder with a specific amount of an Si-containing organic compound and an organic vehicle. Additives such as a plasticizer, an antifoaming agent, and a dispersing agent can be blended in the partition wall-forming coating material.

  The Si-containing organic compound must be blended within a range of 0.3 to 10 parts by weight with respect to 100 parts by weight of the inorganic powder. If the Si-containing organic compound is less than 0.3 parts by weight, adhesion to the photoresist cannot be expected, whereas if it exceeds 10 parts by weight, the Si-containing organic compound is excessive with respect to the inorganic powder, When the humidity is high, it hydrolyzes and modifies the resin, so the grinding speed by sandblasting is slowed down.

  A known method such as a roll mill, a ball mill, a bead mill, or a roller mill can be used for manufacturing the partition wall forming coating.

  In this invention, in order to mix | blend Si containing organic compound with the coating material for barrier rib formation, you may add after mixing with an inorganic powder previously, and you may add to a coating material for barrier rib formation directly as it is.

  When the Si-containing organic compound is mixed with the inorganic powder in advance, it must be mixed only with the inorganic powder and the Si-containing organic compound. The Si-containing organic compound is a liquid, but it is necessary to stir for half a day or more in order to mix the inorganic powder and the Si-containing organic compound uniformly. For the stirring, a known powder mixing method such as a ball mill can be used.

  When water is added during mixing, the liquid increases with respect to the inorganic powder, so that the mixture becomes homogeneous at the time of mixing, but eventually intense aggregation occurs. As described above, it is sufficient that the water of the inorganic powder is adsorbed on the surface, and it must be avoided that the amount of water exceeds 1% by weight.

5). Forming method of partition wall The partition wall forming method of the present invention is obtained by applying the coating material of the present invention to a display device substrate to form a partition pattern, then forming a desired partition shape by sandblasting, and finally baking. Is the method.

  That is, using a display device barrier rib forming coating, after applying a photoresist layer on a dry body obtained by drying on one surface of the substrate, when forming the barrier rib pattern, unnecessary portions are sandblasted. Remove and finally fire.

  The procedure (a)-(g) which forms a partition using the coating material of this invention is demonstrated concretely using FIG.

  (A) First, a dielectric (15) is formed on a glass substrate (10) on which address electrodes (not shown) are formed to form a lower structure.

(B) Next, the partition wall forming coating layer (20) of the present invention is applied on the lower structure of the glass substrate. The layer may be applied at once or may be applied in several times.
The partition wall-forming coating can be applied by screen printing as well as by a die coater or roll coater. The viscosity suitable for coating with a die coater or a roll coater is preferably 100 Pa · s or less at a rotational speed of a Brookfield rotational viscometer HBT type of 10 / min. When the viscosity exceeds 100 Pa · s, the fluidity becomes poor and application is difficult. A particularly preferred coating layer thickness is in the range of 150 to 250 μm.
After forming the paint layer, it is dried by heating to 100 to 150 ° C. to obtain a dried product.

(C) Next, a photoresist layer (21) is laminated on the dried body using the photoresist composition.
As a photoresist composition, a well-known thing can be used without a restriction | limiting in particular, For example, a negative photoresist composition, a positive photoresist composition, etc. can be mentioned. As the positive photoresist composition, for example, a photo-soluble group-generating composition using a 1,2-naphthoquinonediazide compound, an o-nitrobenzyl compound or the like, a photoacid generation / acid using an onium salt, etc. Examples include decomposable compositions. The negative photoresist composition contains, for example, an ethylenically unsaturated compound, a carboxyl group-containing film property-imparting polymer and a photopolymerization initiator as essential components, and in addition, dyes or pigments and other additives as necessary. And a photopolymerizable composition containing an organic solvent.

  (D) A photoresist pattern (22) is formed by covering the laminate with a photomask having a line and space pattern and irradiating light (ultraviolet rays). This photoresist pattern (22) corresponds to the area of the dry body layer that should remain after sandblasting (etching).

(E) Thereafter, a sand blaster nozzle is installed above the photoresist layer, and the abrasive material and air are simultaneously sprayed from the nozzle.
The abrasive material collides with the dry body layer in the region where the photoresist layer is not formed, and scrapes off the layers other than the photoresist pattern (22). The higher the average grinding speed of unnecessary parts by sandblasting, the higher the work efficiency. An average grinding speed of 10 μm / second or less is not preferable because the process is significantly delayed. By this sandblasting, a dry body (23) serving as a partition remains.

  (F) Then, the photoresist layer left on the dried body is removed by treatment with a predetermined solvent and washed with water.

(G) Finally, the dried body thus formed is fired to complete the partition. For firing, a general firing furnace used for manufacturing a normal thick film hybrid IC can be used.
As general firing conditions, firing is preferably performed at a temperature from a temperature 50 ° C. lower than the softening point of the glass powder to a softening point, that is, 450 ° C. to 600 ° C. for 3 to 20 minutes under a condition of exhausting air. If the firing temperature is too low, the glass powder is not sufficiently sintered, so that sufficient strength as a PDP partition cannot be obtained. On the other hand, if the firing temperature is too high, the material melts and flows, and a PDP partition wall having a desired shape cannot be obtained. A particularly preferable firing temperature is from a temperature 30 ° C. lower than the softening point of the glass to the softening point. There is an intimate correlation between the firing temperature conditions and the thermal properties of the glass powder and inorganic oxide powder in the partition wall-forming coating material. Must be corrected.

  According to the present invention, the line width of the partition formed by the photoresist can be narrowly formed to 100 μm or less, and can be set to 60 to 100 μm. When the line width of the partition wall exceeds 100 μm, a high quality PDP cannot be obtained.

  As described above in detail based on the formation of the partition walls of the PDP, the partition wall forming paint of the present invention is not limited to the PDP. For example, the partition walls of a display device having partition walls such as a fluorescent display tube and a field emission display. It can be widely used as a paint for forming.

  Examples of the present invention and comparative examples are shown below, but the present invention is not limited to these examples.

The softening point (glass transition point) of the glass powder was measured by TG-DTA (TG / DTA320 type manufactured by Seiko Electronics Co., Ltd.), and the particle size was measured by Microtrac (registered trademark).
In addition, the average grinding speed during sandblasting was measured using a sandblasting device SGK-4LD-401 manufactured by Fuji Seisakusho. The distance between the nozzle and the substrate was 200 mm, the pressure was 0.2 MPa, and # 600CaCO ₃ was used as the abrasive.

(Examples 1-4) (Comparative Examples 1-2)
Glass powder and paint were prepared by the following method, and subsequently, the obtained paint was applied to a substrate and dried to obtain a dry body of a partition wall-forming paint. Photoresist was laminated thereon, a pattern was formed, unnecessary portions were sandblasted, and a dry body serving as a partition was left, and the performance was evaluated by a method described later. The photoresist was washed and removed by washing with water, and then baked to produce a partition wall.
(1) Preparation of glass powder and paint The glass was melted at 1300 ° C., rapidly cooled, and pulverized with a ball mill. Table 1 shows the softening point, particle size, and the like of the obtained glass powder.
In the present invention, inorganic powder containing 0.5% by weight of water was used (the fact that water was adsorbed on the surface of the inorganic powder was observed with TG-DTA). In order to adsorb water to the inorganic powder, the inorganic powder was pulverized and stored under conditions of a temperature of 18 to 27 ° C. and a relative humidity of 40 to 60%.
The organic vehicle was prepared by mixing 15% by weight of methacrylic resin (Mw: 160,000) as an organic resin and 85% by weight of terpinol as a solvent and heating to 60 ° C.
As the inorganic powder, glass powder, alumina powder, and titania powder blended in a composition of 83: 13: 4 (weight ratio) were used. To this inorganic powder 100% by weight, an organic vehicle 40% by weight, Si-containing organic compound ( 3-Methacryloxypropyltrimethoxysilane) was blended as shown in Table 2 and mixed with a roll mill to obtain a partition wall forming coating material.
(2) Formation of partition walls A partition wall-forming coating material was applied to a substrate, and a dried product having a film thickness of 200 μm was obtained in an IR drying furnace at a peak condition of 120 ° C. × 30 minutes. A photoresist (BF-704, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was laminated on the dried product on a hot plate heated to 100 ° C.
After lamination, the photomask pattern was baked on the resist by irradiating UV (H ray) 150 mJ / cm ² with a FES-10BCW-XY03 type exposure machine manufactured by USHIO through a photomask having a line and space pattern.
The line and space pattern consists of 10 lines of 40 μm width and a space of 100 μm width between each line, 10 lines of 50 μm width and a space of 100 μm width between each line, 10 lines of 60 μm width and each line. Space of 100 μm width, 10 lines of 80 μm width and a space of 100 μm width between each line, 10 lines of 100 μm width and a space of 150 μm width between each line, 10 lines of 150 μm width and a width between each line The space was 150 μm, and the length of each line was 20 mm.
(3) Performance measurement After exposure to the photoresist, development was performed while flowing a 0.5 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. for 1 minute in the photoresist. After the development, pure water at room temperature was passed for 1 minute to wash the alkaline aqueous solution. Thereafter, the remaining photoresist lines were visually confirmed. The line width of the photoresist is at least 100 μm or less, preferably 80 μm or less.
The average grinding speed was determined from the time until the dried body (200 μm film thickness) of the partition wall forming coating material was ground by sandblasting and penetrated through the dried body.
The dried product of the partition wall-forming coating material on which the exposed and developed photoresist pattern is formed is immersed in a stripping solution (50 ° C., 3 wt% triethanolamine aqueous solution) for 20 seconds, and then pure water at room temperature And whether or not the photoresist was peeled off was visually confirmed.

(Reference Example 1)
A coating material was prepared in the same manner as in Example 1 except that the water content of the inorganic powder was changed to 5% by weight.

"Evaluation"
From these results, as in Examples 1 to 4, a desired amount of PDP barrier ribs can be formed by sandblasting even when glass powder containing no lead is blended with a specific amount of Si-containing organic compound in glass powder. I understand that. On the other hand, as in Comparative Examples 1 and 2, if a specific amount of Si-containing organic compound is not blended, the resist line width cannot be narrowed, or the average grinding speed is reduced and a desired PDP partition cannot be formed. I understand that. Further, in Reference Example 1, since the amount of water was too large, the inorganic powder aggregated and a paint was not obtained.

It is explanatory drawing which shows the structure of a general PDP. It is explanatory drawing which shows the procedure which forms a PDP partition by the method of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Glass substrate 11 Transparent electrode 12 Bus electrode 13 Address electrode 14 MgO film | membrane 15 Dielectric 16 Partition 17 Phosphor 20 Paint layer 21 Photoresist layer 22 Resist pattern 23 Dry body

Claims (5)

A resist film having a desired pattern is formed on a partition wall-forming coating layer having a predetermined thickness placed on a substrate, and then an unnecessary portion of the partition wall-forming coating layer is removed by sandblasting. In the method of forming the partition wall,
The partition wall-forming coating material contains an inorganic powder (A), an organic vehicle (B), and an Si-containing organic compound (C), and the content of the Si-containing organic compound (C) is 100 weights of the inorganic powder (A). The method of forming a display device partition wall is 0.3 to 10 parts by weight with respect to the part. The method for forming a display device partition according to claim 1, wherein the glass powder is SiO ₂ —B ₂ O ₃ —ZnO—alkali glass not containing lead.   The organic vehicle (B) includes at least one resin selected from ethyl cellulose, nitrocellulose, acrylic, styrene, or butyral, terpinol, dihydroterpinol, butyl carbitol acetate, butyl carbitol, or 2,2,4- The method for forming a display device partition according to claim 1, comprising at least one solvent selected from trimethyl-1,3-pentanediol monobutyrate.   The method for forming a display device partition according to claim 1, wherein the Si-containing organic compound (C) is silane or silazane having a molecular weight (Mw) of 500 or less.   The inorganic powder (A), the organic vehicle (B) and the Si-containing organic compound (C) are contained, and the content of the Si-containing organic compound (C) is 0.3 with respect to 100 parts by weight of the inorganic powder (A). The coating material for forming a display device partition wall used in the method according to any one of claims 1 to 4, wherein the coating amount is 10 to 10 parts by weight.

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