JPH1165086A - Formation of pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a forming method capable of providing an intended ideal pattern having no bias of an inorganic pattern such as phosphor resulting from even contraction in burning, and particularly provide a method for forming the multicolor fluorescent face of a plasma display panel(PDP). SOLUTION: In the case of exposure of a mineral-containing photosensitive resin composition R containing mineral such as phosphor, a pattern mask M having a fine shield portion M1 ' of a resolution limit or less provided in a non-shield portion M0 is used as the pattern mask M comprising the non-shield portion M0 and the shield portion M1 , and the mineral-containing photosensitive resin composition R containing the mineral is exposed via the pattern mask M. Thereby, a half cured portion R1 ' is formed in a cured portion R1 by the exposure of the composition R. After the exposure, developing is conducted, and final burning is conducted.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an inorganic pattern, and more particularly to a method for forming a plasma display panel (P).
DP) and a method for forming a multicolor phosphor screen.

[0002]

2. Description of the Related Art Recently, various flat panel displays have been actively developed, and among them, a plasma display panel (PDP) has received a great deal of attention. This is PDP
Is most suitable for use in wall-mounted televisions and various electronic signage devices.

In a color PDP, a phosphor for displaying a color is embedded in a discharge cell, and the phosphor emits light by ultraviolet rays generated from a sealing gas by discharge from an applied voltage to electrodes above and below the cell. . The partition of the cell includes a stripe-shaped partition or a grid-shaped partition depending on the type of the PDP. In some cases, there are circular cells surrounded by partition walls.

A method of embedding a phosphor in cells of a substrate provided with partition walls is described in, for example, JP-A-2-155142. That is, in the publication, after applying a photosensitive slurry containing a phosphor on the back surface of the front plate,
It is stated that the film was exposed through a photomask, and was further developed and fired, and that a phosphor screen was also formed on the wall surface of the partition (barrier) for the purpose of increasing the brightness. In the invention of the publication, as an advantageous method for forming a phosphor screen on the wall surface of the latter type of partition,
A method of filling the phosphor slurry liquid in the cell partition, immediately tilting the back plate, leaving the phosphor contained in the slurry liquid to settle on the cell partition, and then drying and curing the phosphor screen. Has adopted. The filling of the phosphor slurry liquid into the cell partition walls is performed by a method of filling with a spray, a screen printing method, a method of pouring the phosphor slurry and scraping it with a rubber squeegee (claims 2 and 4). (See upper left column).

Japanese Patent Application Laid-Open No. Hei 6-273 filed by the present applicant
No. 925 discloses a photoresist film in which a photosensitive resin composition containing a phosphor is laminated on a base film, and that the photoresist film is used as a material for forming a pattern of the phosphor in manufacturing a fluorescent display. It is shown. This method uses a phosphor-containing dry film (photoresist film) that can be handled by a bonding method, instead of a conventional liquid photoresist in which a phosphor is dispersed. This publication states that in order to form a full-color PDP,
Repeating exposure to baking using a photoresist film containing each of red, blue, and green phosphors, and a PD in which cells are previously formed by glass partition walls
There is also a statement that the steps from exposure to baking can be performed on the P flat substrate using the above photoresist film.

[0006]

When phosphors of respective colors are embedded in cells of a substrate provided with partition walls, it is necessary to uniformly expose the phosphor-containing resin composition in the cells according to a conventional method. In addition, due to shrinkage during firing, the phosphor pattern tends to be biased toward one side of the cell or one side of the partition wall, and an intended ideal pattern may not be obtained.

In the invention of Japanese Patent Application Laid-Open No. 2-155142, a phosphor slurry solution is filled in a cell partition, and a back plate is tilted immediately after the phosphor plate is settled until the phosphor contained in the slurry liquid settles on the cell partition. A method of curing the phosphor screen after leaving it to stand still is adopted, but this method is a special method of fixing the phosphor only to the partition walls, so it is a general-purpose PDP
In addition, there is a problem that the operation is extremely complicated and control is difficult.

In this background, the present invention provides a method for forming a pattern in which an inorganic pattern such as a fluorescent substance is not biased even by shrinkage during firing and an intended ideal pattern can be obtained, particularly a plasma display panel (PDP). It is an object of the present invention to provide a method for forming a multicolor phosphor screen of the above).

[0009]

According to the method of forming a pattern of the present invention, an inorganic-containing photosensitive resin composition containing an inorganic substance is provided.
Upon exposure of the (R), a non-shielding portion (M ₀₎ and the shield portion (M ₁₎ from become unshielded portion as a pattern mask (M) (M ₀₎ resolution limit or less fine shielding portion in the (M ₁ ′), and the inorganic-containing photosensitive resin composition through the pattern mask (M).
By performing the exposure of (R), a semi-cured portion (R ₁ ′) is formed in the cured portion (R ₁ ) of the composition (R) by exposure, and after the exposure, development is performed. And baking.

The method for forming a pattern according to the present invention, which has a more specific purpose, comprises an inorganic-containing photosensitive resin containing an inorganic substance comprising a phosphor on a substrate (S) in which empty cells are formed by partition walls (W). Filling the empty cells by applying the composition (R), and curing the inorganic-containing photosensitive resin composition (R) filling the empty cells by exposing through the pattern mask (M). To perform, after exposure, development, and finally baking, thereby forming the phosphor screen of the plasma display panel, and, at the time of the exposure, the non-shielding part (M ₀ ) and the shielding part ( M ₁ ) and a pattern mask (M) provided with a fine shielding portion (M ₁ ′) below the resolution limit in the non-shielding portion (M ₀ ), and through the pattern mask (M) Inorganic-containing photosensitive resin composition
By exposing (R), a semi-cured portion (R ₁ ′) is formed in a cured portion (R ₁ ) of the composition (R) by exposure.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

<Formation of Pattern Mask (M) and Pattern>
In the present invention, as a pattern mask (M) including a non-shielding portion (M ₀ ) and a shielding portion (M ₁ ), a fine shielding portion (M ₁ ′) having a resolution equal to or less than the resolution limit in the non-shielding portion (M ₀ ). ) Is used. The pattern of the fine shielding part (M ₁ ') below the resolution limit is line-shaped,
Dot shape (dots can be any shape such as circle or square)
And so on.

When the inorganic-containing photosensitive resin composition (R) containing an inorganic substance is exposed through the pattern mask (M), the cured portion (R ₁ ) of the composition (R) is semi-cured by the exposure. (R
₁ ') can be formed. Since the semi-cured portion (R ₁ ′) is partially eluted by development, the cured portion (R ₁ ) formed by exposure has a shape having a cut in a cross-sectional view after development.
When this is finally fired, the hardened portion (R ₁ ) is separated from the cut portion when the hardened portion (R ₁ ) shrinks, and the fired inorganic material can be fixed at a predetermined position in a desired pattern.

<Formation of Phosphor Screen of Plasma Display Panel> Next, a case where the pattern forming method of the present invention is applied to the formation of a phosphor screen of a plasma display panel (PDP) will be described.

In a full-color PDP, an inorganic-containing photosensitive resin composition (R) containing an inorganic substance composed of a phosphor of each color is applied to a substrate (S) in which empty cells are formed by partition walls (W). Then, empty cells are sequentially filled.

In a typical case, in the case of the AC drive type, the width is about 50 to 100 μm and the height is 100 to 200 μm.
m is formed in parallel with a gap of about 100 to 200 μm, and in the case of a DC drive type, one side is 100 to 20 μm.
Form a square of about 0 μm. In the case of DC drive type,
In general, in addition to the empty cell for the phosphor, an empty cell for a space where the embedding of the phosphor is not required is required.

The partition wall (W) is provided on the substrate (S) by an appropriate method such as a printing method, an additive method, a sand blast method, and a photosensitive paste method. The printing method is
This is a method in which thick film printing by screen printing and drying are repeated a number of times on a substrate, and finally baked to form partition walls.
The additive method involves laminating a photosensitive film on a substrate, exposing it through a mask, developing it, forming a resist, embedding partition walls in the gaps between the resist, drying, removing the resist, Finally, baking is performed to form partition walls. In the sand blast method, a layer of a partition material is provided on a substrate, a photosensitive film is further laminated thereon, exposed through a mask, developed, and further developed to reach the partition material, and then blasted. This is a method of forming a partition by cutting a partition material under the resist opening, removing the resist, and finally performing baking. The photosensitive paste method is a method in which a mixture of a photosensitive paste and a rib material is applied to a substrate, dried, exposed through a mask, developed, and finally fired to form a partition. . Although these partition wall forming methods have advantages and disadvantages, the additive method and the sand blast method are advantageous from a comprehensive point of view.

In order to fill the inorganic (phosphor) -containing photosensitive resin composition (R) into the empty cells formed by the partition walls (W), various methods are adopted. For example, (a) a method of sequentially filling cells for a specific color with a phosphor-containing photosensitive resin composition (R) of a specific color by a screen printing method or the like. A cell is filled with a red phosphor-containing photosensitive resin composition (R), and then a green phosphor-containing photosensitive resin composition is placed in a cell for green.
(R), and finally filling the cell for blue with the blue-containing phosphor-containing photosensitive resin composition (R), (b) using a phosphor-free photoresist film,
(S) A method of sequentially forming empty cells for a specific color in cells between the partition walls (W) on the upper side, and sequentially embedding the phosphor-containing photosensitive resin composition (R) in the resulting empty cells, Specifically, using a photoresist film containing no phosphor, only the cells for red are opened, and the red phosphor-containing photosensitive resin composition (R) is embedded therein, and in the same manner, green For embedding the opening and the green phosphor-containing photosensitive resin composition (R) for blue and the opening for blue and embedding the blue phosphor-containing photosensitive resin composition (R), (c) Photo A method of sequentially filling a cell for a specific color with a phosphor-containing photosensitive resin composition (R) of a specific color using the phosphor-containing photosensitive resin composition (R) in the form of a resist film More specifically, first use a red phosphor-containing photoresist film. A red phosphor-containing photosensitive resin composition (R) is embedded in a cell for red, and then a green phosphor-containing photosensitive resin composition (R) is placed in a cell for green using a green phosphor-containing photoresist film. And finally embedding the blue phosphor-containing photosensitive resin composition (R) in a cell for blue using a blue phosphor-containing photoresist film.

Hereinafter, the phosphor-containing photosensitive resin composition (R) in the form of a photoresist film will be described in more detail, taking the case (c) of the above exemplified methods as an example.

As the above-mentioned photoresist film, a phosphor-containing photosensitive resin composition (R) is applied to a base film surface such as a polyester film, a polypropylene film and a polystyrene film, and then a polyethylene film is applied from the coated surface. And a protective film such as a polyvinyl alcohol film or a polyester film, which is used as a laminate for a dry film resist. At this time, the thickness of the phosphor-containing photosensitive resin composition (R) layer is usually 10 to 200 μm in many cases.

The composition of the phosphor-containing photosensitive resin composition (R) layer is typically a composition comprising a base polymer, an ethylenically unsaturated compound, a photopolymerization initiator and a phosphor. Used.

Examples of the base polymer include an acrylic resin, a polyester resin, a polyurethane resin, and a polyvinyl alcohol resin. Among them, (meth) acrylate is a main component, and if necessary, an ethylenic resin is used. Acrylic copolymers obtained by copolymerizing saturated carboxylic acids and other copolymerizable monomers are important. An acetoacetyl group-containing acrylic copolymer can also be used.

Examples of the ethylenically unsaturated compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate. ) Acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol Di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2,2
-Bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-
3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, glycerin polyglycidyl ether poly A polyfunctional monomer such as (meth) acrylate is used. An appropriate amount of the following monofunctional monomers can be used together with these polyfunctional monomers.

As the monofunctional monomer, for example, 2-
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl Phthalate,
3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate,
Examples include phthalic acid derivative half (meth) acrylate and N-methylol (meth) acrylamide.

Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, benzyl dimethyl ketal, dibenzyl, diacetyl, anthraquinone and naphthoquinone. 3,3'-dimethyl-4-methoxybenzophenone, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-diethylaminobenzophenone, pivaloinethyl Ether, 1,1-dichloroacetophenone, pt-butyldichloroacetophenone, hexaarylimidazole dimer, 2,2′-
Bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-
Diethylthioxanthone, 2,2′-diethoxyacetophenone, 2,2′-dimethoxy-2-phenylacetophenone, 2,2′-dichloro-4-phenoxyacetophenone, phenylglyoxylate, α-hydroxyisobutylphenone, dibenzosparone, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-
1-propanone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, tribromophenylsulfone, tribromomethylphenylsulfone and the like are used.

As the phosphor, rare earth oxyhalide or the like can be used.
It is preferable that the parent is activated by an activator.
For example, as an ultraviolet excitation type,_TwoO_Three: Eu, YVO_Four: Eu, (Y, Gd) BO
_Three: Eu, ・ Blue as Sr_Five(PO_Four)_ThreeCl: Eu, BaMgAl₁₄O
_{twenty three}: Eu, BaMgAl₁₆O₂₇: Eu, Zn as green_TwoGeO_Two: Mn, BaAl₁₂O₁₈: Mn
 , Zn_TwoSiO_Four: Mn, LaPO_Four: Tb, etc. Other phosphors include:-Red, Y_TwoOsS: Eu, γ-Zn_Three(PO_Four)_Two: M
n, (ZnCd) S: Ag + In_TwoO_Three・ Blue: ZnS: Ag + red pigment, Y_TwoSiO_Three:
Cs, as green ones, ZnS: Cu, Al, ZnS: Au, Cu, Al,
(ZnCd) S: Cu, Al, Zn_TwoSiO _Four: Mn, As, Y_ThreeAl_FiveO₁₂: Ce, Gd_TwoO
_TwoS: Tb, Y_ThreeAl_FiveO₁₂: Tb, ZnO: Zn and the like.

The ratio of the ethylenically unsaturated compound to 100 parts by weight of the base polymer is preferably, for example, 10 to 200 parts by weight (particularly, 40 to 150 parts by weight). If the amount of the ethylenically unsaturated compound is too small, curing may be poor, the flexibility may be reduced, and the development speed may be delayed. If the amount is too large, the adhesion may be increased, cold flow may occur, and the peeling speed of the cured resist may be reduced. The photopolymerization initiator is suitably used in an amount of about 1 to 20 parts by weight based on 100 parts by weight of the total of the base polymer and the ethylenically unsaturated compound. The phosphor is often used in an amount of 10 to 500 parts by weight based on 100 parts by weight of the total amount of the base polymer and the ethylenically unsaturated compound.

In the phosphor-containing photosensitive resin composition (R),
In addition, dyes, adhesion promoters, plasticizers, scratch resistance promoters, compatibilizers, antioxidants, thermal polymerization inhibitors, solvents, surface tension modifiers, stabilizers, chain transfer agents, defoamers, Additives such as a flame retardant, a fluidity improver, a rheology improver, an antistatic agent, and a conductivity imparting agent can be appropriately added.

For laminating the photoresist film on the substrate (S), a laminating method using a hot roll is usually employed. In this case, if necessary, a convex shape conforming to the concave shape of the cell from above is used. The photoresist film can be made to follow the cell shape by pressing with a mold or the like having the above.

In bonding, the adhesive strength between the base film of the photoresist film and the phosphor-containing photosensitive resin composition (R) layer and the adhesion between the protective film and the phosphor-containing photosensitive resin composition (R) layer After comparing the strength and peeling off the lower adhesive film, the phosphor-containing photosensitive resin composition
The side of the (R) layer is pasted on a substrate (S) provided with a partition (W) in advance, and the other film is exposed with a pattern mask (M) adhered thereto. At this time, if necessary, the film remaining on the resist film can be peeled off and a photoresist film can be further stacked. When the phosphor-containing photosensitive resin composition (R) layer has no tackiness, the other film is peeled off, and then the pattern mask (M) is replaced with the phosphor-containing photosensitive resin composition (R). ) The layer can be exposed in direct contact with the layer.

In the present invention, as described above, the pattern mask (M) including the non-shielding portion (M ₀ ) and the shielding portion (M ₁ ) is provided in the non-shielding portion (M ₀ ). The _one provided with a fine shielding portion (M ₁ ′) below the resolution limit is used. The pattern of the fine shielding portion (M ₁ ′) below the resolution limit is a line shape, a dot shape, or the like.

By exposing the phosphor-containing photosensitive resin composition (R) layer through the pattern mask (M), the composition becomes
A semi-cured portion (R ₁ ′) can be formed in the cured portion (R ₁ ) by exposure of the (R) layer.

Since the exposure is performed for the cell portion for the first color of the bonded photoresist film, a pattern mask corresponding to the cell portion is used. Exposure is usually performed by ultraviolet irradiation, and as a light source at that time, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp, or the like is used. After the irradiation with ultraviolet rays, heating can be performed as needed to complete the curing. This exposure cures the first cell portion of the bonded photoresist film.

After exposure, a phosphor-containing photosensitive resin composition
(R) If there is a film on the layer, the film is peeled off and developed. The development is usually carried out using a dilute aqueous solution having a concentration of about 0.1 to 5% by weight of an alkali such as sodium carbonate or potassium carbonate or a concentration around the same.

By this development, the cell for the first color is filled with the cured product of the phosphor-containing photosensitive resin composition (R) of the first color, and the other cells become empty cells. And the semi-cured part (R ₁ ′) in the cured part (R ₁ ) of the cell for the first color is
Since a part is eluted by the development, the cured portion (R ₁ ) by the exposure has a shape like a cut in a sectional view after the development.

By performing such a series of operations of laminating, exposing, and developing the photoresist film for the cell for the second color and the cell for the third color,
The first cell contains a phosphor-containing photosensitive resin composition of a first color.
(R) is filled and cured, the second cell is filled and cured with the phosphor-containing photosensitive resin composition (R) of the second color, and the third cell is phosphor of the third color. The photosensitive resin composition (R) is filled and cured. In addition, like DC type color PDP,
If there is a cell that does not require the embedding of the phosphor, that cell is left empty.

After performing the above operations, the entire substrate (S) is subjected to a firing step. The firing temperature is about 420-550 ° C,
Preferably, it is usually about 450 to 500 ° C. By firing, the phosphor-containing photosensitive resin composition in the cell
The organic components in the cured product of (R) are scattered by thermal decomposition and
The phosphor is fixed to the wall surface of (W) and / or the bottom surface of the cell. At this time, when the cured portion (R ₁ ) shrinks, separation occurs from the cut portion, and the fired phosphor can be fixed at a predetermined location in an intended pattern. Thereby, a multicolor phosphor screen of the target color PDP is formed.

[0038]

The present invention will be further described with reference to the following examples. Hereinafter, “parts” and “%” are expressed on a weight basis.

Embodiment 1 FIG. 1 is an explanatory view schematically showing steps when the method of the present invention is applied to the formation of a multicolor fluorescent screen of an AC-driven color PDP.

<Preparation of Substrate (S) with Partition (W)> Substrate (S)
On the top, a partition (W) with a width of 70 μm and a height of 100 μm has 150
Ones formed in parallel in stripes with a gap of μm were prepared ((a) in FIG. 1).

<Photoresist Film> As an inorganic (phosphor) -containing photosensitive resin composition (R) containing an inorganic substance composed of a phosphor, the following base polymer (46 parts), ethylenically unsaturated compound (54 parts), photopolymerization initiation Using a mixture of 8 parts of the agent and 50 parts of the phosphor, a photoresist film having a layer structure of polyester support film / phosphor-containing photosensitive resin composition (R) layer / polyethylene protective film was prepared.

Base polymer: The copolymerization ratio of methyl methacrylate / n-butyl methacrylate / 2-ethylhexyl acrylate / methacrylic acid is 55 by weight.
/ 8/15/22 (acid value: 143.3, glass transition point: 66.3 ° C., weight average molecular weight: 80,000).

Ethylenically unsaturated compound: A mixture of trimethylolpropane triacrylate / polyethylene glycol (molecular weight: 600) dimethacrylate / ethylene oxide-modified phthalic acrylate (manufactured by Kyoeisha Yushi Kogyo Co., Ltd.) in a weight ratio of 20/10/6. .

Photoinitiator: benzophenone 8.0 parts,
0.15 parts of p, p'-diethylaminobenzophenone, 2,
2-bis (o-chlorophenyl) -4,5,4 ', 5'
A mixture of 1.0 part of tetraphenyl-1,2'-biimidazole.

Phosphor: Red phosphor "LP-RE1" manufactured by Kasei Opto Co., Ltd., green phosphor "P1G1S" manufactured by Kasei Opto Co., Ltd., and blue phosphor "KX501A" manufactured by Kasei Opto Co., Ltd.

After preheating the above substrate (S) to 60 ° C., the above-mentioned photoresist film obtained by removing the protective film from the photoresist film containing the red phosphor was laminated with a hot roll at 100 ° C. The support film was peeled off. Repeat this operation again,
The red phosphor-containing photosensitive resin composition (R) was made to completely fill the target cell ((a) and (b) in FIG. 1).

Next, a pattern mask (M) was placed on three of the cells such that they were exposed at a ratio of two cells, and parallel light was irradiated at 100 mJ / cm ² to perform exposure ((FIG. 1) C)).

At this time, the pattern mask (M) is
It consists of a non-shielding part (M ₀ ) and a shielding part (M ₁ ), and the non-shielding part (M
₀ ) provided a line-shaped fine shielding portion (M ₁ ′) below the resolution limit. The shielding part (M ₁ ) is
The width of μm and the upper part of the cell other than the cell to be exposed were covered. The line-shaped fine shielding part (M ₁ ′) has a central part between the partition walls (W) of 10 μm width, 20 μm width, and 30 μm width, respectively.
The light was shielded linearly in a width of 40 μm, 50 μm, and 60 μm. An experiment was also conducted without the fine shield (M1 ').

Thereafter, a 1% aqueous sodium carbonate solution (3
The unexposed portion was removed by performing showering at 0 ° C.) under the condition of 1.5 times the minimum developing time (FIG. 1 (d)).

Next, similarly, lamination, exposure and development of the green phosphor-containing photosensitive resin composition (R) layer were carried out (FIG. 1).
(E), (f), (g)), and in the same manner, laminating, exposing, and developing a blue phosphor-containing photosensitive resin composition (R) layer ((h), (h) in FIG. 1). Li), (nu)).

Finally, the substrate (S) thus treated is
After heating at a rate of 4.5 ° C / min, 50
The organic component is volatilized or decomposed and removed by baking under the condition of holding at 0 ° C. for 30 minutes, and the phosphors R, G, and
B was fixed ((l) in FIG. 1).

When the fine shielding portion (M ₁ ′) is set to various widths, the pattern shape of the central line elution portion after development and the shape of the phosphor pattern after firing are as shown in Table 1 below. Was.

[0053]

[Table 1] Fine shielding part (M ₁ ') Pattern of elution part at the center of line Set phosphor pattern after firing (μm) Shape (μm) Shape of pattern 0 Width: 0 Depth: 0 Irregularly separated to left and right 10 Width : 0 Depth: 0 Irregularly separated to the left and right 20 Width: 15 Depth: Follows the U-shape 30 Width: 27 Depth: Follows the U-shape 40 Width: 37 Depth: 70 U-shape Following 50 Width: 48 Depth: 85 Following U-shape 60 Width: 60 Depth: 100 Cell bottom exposed

From Table 1, it can be seen that under the conditions of the first embodiment, when the set width of the fine shielding portion (M ₁ ′) is 20 to 50 μm, it is lower than the resolution limit and the cured portion (R ₁ ) has a semi-cured portion (R ₁ ). R ₁ ') is formed, and when set in this way, the phosphor adheres uniformly to the bottom surface of each cell and the partition (W) surface in a U-shape in cross-section, and is ideal It can be seen that the pattern is formed and a reliable multicolor phosphor screen of the AC type color PDP is formed.

Embodiment 2 FIG. 2 is an explanatory view schematically showing steps when the method of the present invention is applied to the formation of a multicolor fluorescent screen of a DC-driven color PDP. However, FIG. 2 shows only the diagrams corresponding to FIGS. 1A and 1B.

On the substrate (S), a width of 75 μm and a height of 125 μm
A partition wall (W) of m is formed in a grid pattern with a gap of 125 μm (FIG. 2A), and red, green, and blue fluorescent light is applied to each cell according to the first embodiment. Embedding of the body-containing photosensitive resin composition (R), exposure through a pattern mask (M), and development were performed in series, and finally a baking treatment was performed.

The pattern mask (M) used for exposure is composed of a non-shielding portion (M ₀ ) and a shielding portion (M ₁ ), and has a diameter of 30 μm or less below the resolution limit at the center of the non-shielding portion (M ₀ ). The _one provided with a circular dot-shaped fine shielding part (M ₁ ′) was used. As a result, a reliable multicolor phosphor screen of the DC type color PDP was formed with high accuracy, high operability, and high reliability (FIG. 2 (l)).

[0058]

According to the present invention, upon exposure, as a pattern mask (M) composed of a non-shielding portion (M ₀ ) and a shielding portion (M ₁ ), the pattern mask (M ₀ ) has a resolution less than the resolution limit within the non-shielding portion (M ₀ ). By using the one provided with a fine shielding part (M ₁ ′), by exposing the inorganic-containing photosensitive resin composition (R) through the pattern mask (M),
A semi-cured portion (R ₁ ′) is added to a cured portion (R ₁ ) by exposure of the composition (R).
Is formed. At this time, the hardened part (R ₁ )
When the shrinkage occurs, separation occurs from the cut portion, and the fired inorganic substance (such as a phosphor) can be fixed at a predetermined location in an intended pattern. Therefore, the inorganic pattern such as the phosphor is not biased by the shrinkage at the time of firing, and the intended ideal pattern is formed. It is.

As described above, according to the present invention, it is possible to form a reliable multi-color phosphor screen of a color PDP which can be reliably operated with good operability and can easily cope with a high-definition panel. Therefore, the present invention is useful as an industrial method for forming a multicolor phosphor screen of a color PDP.

[Brief description of the drawings]

FIG. 1 is an explanatory view schematically showing steps when a method of the present invention is applied to formation of a multicolor fluorescent screen of an AC-driven color PDP.

FIG. 2 is an explanatory diagram schematically showing steps when the method of the present invention is applied to the formation of a multicolor fluorescent screen of a DC-driven color PDP.

[Explanation of symbols]

(S) ... substrate, (W) ... partition, (M) ... mask, (M ₀ ) ... non-shielding part, (M ₁ ) ... shielding part, (M ₁ ') ... fine shielding part, (R) ... inorganic (Phosphor) -containing photosensitive resin composition, (R ₁ )
(R ₁ ')… Semi-cured part, R, G, B… Phosphor

Claims (5)

[Claims] A non-shielding portion (M ₀ ) and a shielding portion (M ₁ ) for exposing an inorganic-containing photosensitive resin composition (R) containing an inorganic material.
A pattern mask (M) comprising a non-shielding part (M ₀ ) and a fine shielding part (M ₁ ′) below the resolution limit provided in the non-shielding part (M ₀ ),
By exposing the inorganic-containing photosensitive resin composition (R) through the pattern mask (M), a cured part (R ₁ ) of the composition (R) is exposed to a semi-cured part (R ₁ ′). Forming a pattern, developing after exposure, and finally baking. 2. The pattern forming method according to claim 1, wherein the inorganic substance contained in the inorganic-containing photosensitive resin composition (R) is a phosphor. 3. The pattern forming method according to claim 1, wherein the inorganic-containing photosensitive resin composition (R) is handled in the form of a photoresist film. 4. An inorganic-containing photosensitive resin composition (R) containing an inorganic substance composed of a phosphor is applied to a substrate (S) on which empty cells are formed by partition walls (W) to fill the empty cells. That, the inorganic-containing photosensitive resin composition (R) filling the empty cells by exposure through a pattern mask (M), after exposure, development, and finally Baking, thereby forming the phosphor screen of the plasma display panel, and at the time of the above exposure, as a pattern mask (M) comprising a non-shielding part (M ₀ ) and a shielding part (M ₁ ) Using the part (M ₀ ) provided with a fine shielding part (M ₁ ′) below the resolution limit in the part (M ₀ ), the inorganic-containing photosensitive resin composition (R) is exposed through the pattern mask (M). Thereby, a semi-cured portion (R ₁ ′) is formed in the cured portion (R ₁ ) of the composition (R) by exposure. Forming a pattern. 5. An inorganic-containing photosensitive resin composition in an empty cell.
Filling, exposure, and development of (R) are performed in series so that empty cells for each color are filled with the inorganic-containing photosensitive resin composition (R) containing the inorganic material of each color, and the color is obtained. 5. The pattern forming method according to claim 4, wherein a phosphor screen of the plasma display panel is formed.