JPH11271980A - Production of phosphor pattern, photosensitive element for forming phosphor pattern, phosphor pattern and rear surface plate for plasma display panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive element which is capable of forming phosphor patterns having excellent suppression of edge fusion and embeddability into the spaces of a substrate having ruggedness, such as substrate for a PDP, etc., and having high accuracy and a uniform shape at a good yield and workability, the phosphor pattern having the high accuracy, the uniform shape and excellent luminance and a rear surface plate for a plasma display panel having these phosphor patterns. SOLUTION: This process includes respective stages of (I) a stage of forming (A) a photosensitive resin compsn. layer 6 contg. phosphors and (C) a resin layer 8 contg. particulates on a substrate 1 having ruggedness, (II) a stage for imagewise irradiating (C) the resin layer 8 contg. the (C) particulates and (A) the photosensitive resin compsn. layer 6 contg. the phosphors with active light, (III) a stage for forming patterns by removing (C) the resin layer 8 contg. the particulates and selectively removing (A) the photosensitive resin compsn. layer 6 contg. the phosphors and (IV) a stage for removing an org. component by baking.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for manufacturing a phosphor pattern, a photosensitive element for forming a phosphor pattern, a phosphor pattern, and a back plate for a plasma display panel.

[0002]

2. Description of the Related Art Conventionally, as one of flat panel displays, a plasma display panel (hereinafter, referred to as a PDP) capable of performing multicolor display by providing a phosphor which emits light by plasma discharge has been known. In a PDP, a flat front plate and a rear plate made of glass are disposed in parallel and opposed to each other, and both are held at a fixed interval by barrier ribs provided therebetween. And discharges in a space surrounded by the barrier ribs. In such a space, a phosphor for display is applied, and the phosphor is caused to emit light by ultraviolet rays generated from the sealing gas by discharge, so that the light can be visually recognized by an observer.

Conventionally, a method of providing this phosphor is as follows.
A method of applying a slurry liquid or paste in which phosphors of each color are dispersed by a printing method such as screen printing has been proposed, and is disclosed in JP-A-1-115027, JP-A-1-124929, and JP-A-1-124930. And JP-A-2-155142. However, since the above-mentioned phosphor dispersion slurry liquid is liquid, dispersion failure due to precipitation of the phosphor is likely to occur, and when a liquid photosensitive resist is used for the slurry liquid, it is preserved by promoting a dark reaction and the like. It has disadvantages such as poor stability. Furthermore, since printing methods such as screen printing are inferior in printing accuracy, there is a problem that it is difficult to cope with a larger PDP in the future.

In order to solve these problems, a method using a photosensitive element containing a phosphor (also referred to as a photosensitive film) has been proposed (Japanese Patent Laid-Open No. Hei 6-273925).
No.). The method using a photosensitive element means that a photosensitive resin layer containing a phosphor of a photosensitive element composed of a photosensitive resin layer containing a phosphor and a support film is heat-pressed (laminated) to the PDP substrate. Embed in the space, then, using a negative film, imagewise expose to actinic light such as ultraviolet light by photographic methods, then remove the unexposed parts with a developing solution such as an aqueous alkaline solution, and further expose by baking An unnecessary organic component of the photosensitive resin layer containing a part of the phosphor is removed, and a phosphor pattern is formed only on a necessary part. Since a method using such a photosensitive element uses a photographic method, a phosphor pattern can be formed with high accuracy.

However, after a photosensitive resin layer containing a phosphor is formed on the entire uneven surface of the PDP substrate using a photosensitive element, active light is imagewise exposed through a photomask. In the conventional method of developing and baking, the photocurability of the barrier rib wall surface portion on the inner surface of the concave portion is lower than the photocurability of the substrate bottom surface, and the photosensitive resin layer containing the phosphor on the barrier rib wall portion tends to erode during development. Therefore, it has been difficult to form a phosphor pattern with a uniform thickness and a good yield over the inner surface of the concave portion surrounded by the barrier rib wall surface and the substrate bottom surface.

[0006]

According to the first aspect of the present invention, there is provided a method of embedding a substrate having irregularities such as a PDP substrate into a space (in the case of a PDP substrate, the phosphor on the wall surface of the barrier rib and the bottom surface of the space is used). The present invention provides a method for producing a phosphor pattern which is excellent in the formability of a photosensitive resin composition layer to be contained, has a good yield, and can form a phosphor pattern having a uniform shape with high accuracy with a sufficient margin. The invention according to claim 2 provides a method of manufacturing a phosphor pattern which is excellent in workability and environmental safety in addition to the effects of the invention of claim 1.

A third aspect of the present invention provides a method of manufacturing a phosphor pattern which is excellent in workability in addition to the effects of the first or second aspect of the present invention. The invention described in claim 4 provides the effect of the invention described in claim 1 or 2,
It is another object of the present invention to provide a method for producing a phosphor pattern which is excellent in suppressing film loss (erosion of the photosensitive resin layer containing the phosphor on the wall surface of the barrier rib). The invention according to claim 5 is
Another object of the present invention is to provide a method of manufacturing a phosphor pattern which is excellent in workability and photosensitivity in addition to the effects of the invention described in claims 1, 2, 3 and 4.

The invention according to claim 6 is to suppress edge fusion and to embed a substrate having irregularities such as a PDP substrate into a space (in the case of a PDP substrate, the fluorescent material is contained on the barrier rib wall surface and the space bottom surface). The present invention provides a photosensitive element for forming a phosphor pattern, which is capable of forming a phosphor pattern having a uniform shape with a high precision, a good yield and a good workability with a good margin. . The invention described in claim 7 provides a photosensitive element for forming a phosphor pattern, which is excellent in workability and light sensitivity in addition to the effects of the invention described in claim 6.

An eighth aspect of the present invention is to provide a phosphor pattern having a high precision, a uniform shape, and excellent luminance. A ninth aspect of the present invention is to provide a back plate for a plasma display panel provided with a phosphor pattern having high accuracy, a uniform shape, and excellent brightness.

[0010]

According to the present invention, (A) a photosensitive resin composition layer containing a phosphor and (C) a resin layer containing fine particles are formed on a substrate having irregularities. (A) a resin layer containing fine particles (C) and (A)
Irradiating actinic rays imagewise to the photosensitive resin composition layer containing the phosphor, (III) removing the resin layer containing the fine particles (C), and developing the photosensitive resin containing the phosphor (A) by development. The present invention relates to a method for producing a phosphor pattern, comprising: a step of forming a pattern by selectively removing a resin composition layer; and (IV) a step of removing an organic component by baking.

[0011] In the present invention, the step (I) may comprise:
(I ″) For forming a phosphor pattern, comprising (C) a resin layer containing fine particles on a support film, and (A) a photosensitive resin composition layer containing a phosphor thereon. A step of laminating a photosensitive element on a substrate having projections and depressions such that the layer (A) is in contact with the substrate, and forming the layers (A) and (C) on the substrate having projections and depressions. The present invention also relates to a method for producing a pattern.
The process of (III) is repeated to form a multicolor pattern composed of a photosensitive resin composition layer containing a phosphor that emits red, green, and blue, and then the process of (IV) is performed to perform multicolor fluorescence. The present invention relates to a method for producing the phosphor pattern for forming a body pattern. In addition, the present invention relates to a method for producing the phosphor pattern for forming a multicolor phosphor pattern that emits red, green and blue by repeating the steps (I) to (IV).

Further, the present invention provides (A) a photosensitive resin composition layer containing a phosphor, wherein (a) a film-imparting polymer, (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group, (C) a photoinitiator that generates free radicals upon irradiation with active light, and (d) a phosphor.
(C) The present invention relates to a method for producing the phosphor pattern, wherein the resin layer containing fine particles contains a thermoplastic resin.

[0013] Further, the present invention provides a method for manufacturing a semiconductor device comprising:
The present invention relates to a photosensitive element for forming a phosphor pattern, comprising (C) a resin layer containing fine particles and (A) a photosensitive resin composition layer containing a phosphor. Further, the present invention provides (A) a photosensitive resin composition layer containing a phosphor, wherein (a) a film-imparting polymer, (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group, and (c) The photoinitiator for forming a phosphor pattern, comprising: a photoinitiator that generates free radicals upon irradiation with active light; and (d) a phosphor, wherein the resin layer containing (C) fine particles contains a thermoplastic resin. Sexual element.

[0014] The present invention also relates to a phosphor pattern manufactured by the method for manufacturing a phosphor pattern. Also,
The present invention relates to a plasma display panel back plate comprising the above-described phosphor pattern on a plasma display panel substrate.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the substrate having unevenness in the present invention include a substrate for a plasma display panel (substrate for a PDP) on which barrier ribs are formed. Examples of the PDP substrate include a substrate such as a glass plate or a synthetic resin on which electrodes and barrier ribs are formed, which may be subjected to a surface treatment for transparent bonding. For forming the barrier rib, a known material can be used without any particular limitation. For example, a rib material containing silica, a thermosetting resin, a low-melting glass (such as lead oxide), a solvent, or the like can be used.

Further, in addition to the electrodes and barrier ribs, a dielectric film, an insulating film, an auxiliary electrode, a resistor, and the like may be formed on the PDP substrate, if necessary. There is no particular limitation on the method of forming these on a substrate, and for example, on a substrate, evaporation, sputtering, plating, coating,
The electrodes can be formed by a method such as printing, and the barrier ribs can be formed by a method such as a printing method, a sandblast method, or embedding. 1 and 2 are schematic diagrams of a PDP substrate on which barrier ribs are formed. The barrier ribs usually have a height of 20 to 500 μm and a width of 20 to 200 μm.

The shape of the discharge space surrounded by the barrier ribs is not particularly limited, and may be a lattice shape, a stripe shape, a honeycomb shape, a triangular shape, an elliptical shape, or the like, and is usually shown in FIGS. Thus, a grid-like or stripe-like discharge space is formed. 1 and 2, a barrier rib 2 is formed on a substrate 1. In FIG. 1, a grid-like discharge space 3 is formed, and in FIG. 2, a stripe-like discharge space 4 is formed. The size of the discharge space is determined by the size and resolution of the PDP, and in a grid-like discharge space as shown in FIG. 1, the vertical and horizontal lengths are 50 μm to 1 mm.
In a striped discharge space as shown in FIG.
m to 1 mm.

The photosensitive resin composition layer containing the phosphor (A) in the present invention is not particularly limited as long as it is a layer containing a photosensitive resin composition containing a phosphor as an essential component. a) a layer containing a film-imparting polymer, (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group, (c) a photoinitiator that generates free radicals upon irradiation with active light, and (d) a phosphor. Preferred are mentioned.

Examples of (a) a film-imparting polymer, (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group, and (c) a photoinitiator that generates free radicals upon irradiation with active light are described in What is described in 9-265906 can be used.

In addition, since it is necessary to remove organic components by baking when forming a phosphor pattern described later,
Among the photosensitive resin compositions constituting the photosensitive resin composition layer containing the phosphor (A), the photosensitive resin composition other than the phosphor and the binder described later (d) has good thermal decomposability. Need to be For this reason, it is preferable that the photosensitive resin composition other than (d) the phosphor and the binder does not contain any element other than carbon, hydrogen, oxygen and nitrogen as constituent elements thereof.

(D) The phosphor is not particularly limited.
Those mainly composed of ordinary metal oxides can be used. Examples of red-colored phosphors include Y ₂ O ₂ S: Eu and Zn.
₃ (PO ₄ ) ₂ : Mn, Y ₂ O ₃ : Eu, YVO ₄ : Eu,
(Y, Gd) BO ₃ : Eu, γ-Zn ₃ (PO ₄ ) ₂ : Mn,
(ZnCd) S: Ag + In ₂ O and the like. Examples of green-colored phosphors include ZnS: Cu and Zn ₂ S.
iO ₄ : Mn, ZnS: Cu + Zn ₂ SiO ₄ : Mn, G
d ₂ O ₂ S: Tb, Y ₃ Al ₅ O ₁₂ : Ce, ZnS: Cu,
Al, Y ₂ O ₂ S: Tb, ZnO: Zn, ZnS: Cu,
Al + In ₂ O ₃ , LaPO ₄ : Ce, Tb, BaO · 6
Al ₂ O ₃ : Mn and the like. Examples of blue-colored phosphors include ZnS: Ag, ZnS: Ag, Al, and Z.
nS: Ag, Ga, Al, ZnS: Ag, Cu, Ga,
Cl, ZnS: Ag + In ₂ O ₃ , Ca ₂ B ₅ O ₉ Cl: E
^{u 2+, (Sr, Ca,} Ba, Mg) 10 (PO 4) 6 C1 2: E
u ²⁺ , Sr ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu ²⁺ , BaMgAl ₁₀ O
₁₇ : Eu ²⁺ , BaMgAl ₁₄ O ₂₃ : Eu ²⁺ , BaMgA
l ₁₆ O ₂₆ : Eu ^{2+ and the} like.

The particle size of the phosphor (d) in the present invention is as follows:
0.1 to 20 μm, preferably 1 to 15 μm
Is more preferable, and particularly preferably 2 to 8 μm. When the particle size is less than 0.1 μm, the luminous efficiency tends to decrease, and when it exceeds 20 μm, the dispersibility tends to decrease. Further, the shape of the phosphor (d) in the present invention is preferably spherical, and the surface area thereof is preferably small.

The amount of component (a) is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, based on 100 parts by weight of the total of components (a) and (b). preferable. When the compounding amount is less than 10 parts by weight, when the photosensitive element is supplied in a roll form,
By exuding the photosensitive resin composition containing the phosphor from the end of the roll (hereinafter referred to as edge fusion),
When laminating the photosensitive element, it becomes difficult to draw out from the roll, or the extruded portion is partially and excessively embedded in the space of the PDP substrate, which causes a problem such as a remarkable decrease in manufacturing yield, and a problem such as film formation. When the amount exceeds 90 parts by weight, the sensitivity tends to be insufficient.

The amount of the component (b) is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, based on 100 parts by weight of the total of the components (a) and (b). preferable. If the amount is less than 10 parts by weight, the sensitivity of the photosensitive resin composition containing the phosphor tends to be insufficient, and if it exceeds 90 parts by weight, the photocured product tends to become brittle, and In the case of a photosensitive element, the photosensitive resin composition containing the phosphor tends to exude from the end due to the flow, and the film-forming property tends to be reduced.

Component (c) is added in an amount of 0.01 to 3 with respect to 100 parts by weight of the total of components (a) and (b).
It is preferably 0 parts by weight, more preferably 0.1 to 20 parts by weight. When the amount is less than 0.01 part by weight, the sensitivity of the photosensitive resin composition containing the phosphor tends to be insufficient, and when the amount exceeds 30 parts by weight, the photosensitive resin composition containing the phosphor tends to be insufficient. The absorption of active light on the exposed surface of the object tends to increase, and the internal light curing tends to be insufficient.

The amount of component (d) is as follows:
The total amount of the components (b) and (c) is preferably 10 to 300 parts by weight based on 100 parts by weight, and 50 to 300 parts by weight.
250 parts by weight, more preferably 70 to 200 parts by weight.
It is particularly preferred to use parts by weight. This blending amount is 10
If the amount is less than part by weight, the luminous efficiency tends to decrease when light is emitted as a PDP. If the amount exceeds 300 parts by weight, the film formability or flexibility decreases when the photosensitive element is used. Tend.

In the present invention, the photosensitive resin composition constituting the (A) phosphor-containing photosensitive resin composition layer does not increase in viscosity for a long period of time and has good storage stability.
A compound having a carboxyl group can be contained. As the compound having a carboxyl group, for example,
Examples include saturated fatty acids, unsaturated fatty acids, aliphatic dibasic acids, aromatic dibasic acids, aliphatic tribasic acids, aromatic tribasic acids, and the like.

Specifically, for example, formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, propionic acid,
Capric, undecanoic, lauric, tridecanoic, myristic, pentadecanoic, palmitic, heptadecanoic, stearic, nonadecanoic, arachidic, palmitooleic, oleic, elaidic, linolenic, linoleic, Oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, monomethyl malonate,
Monoethyl malonate, succinic acid, methylsuccinic acid, adipic acid, methyladipic acid, pimelic acid, suberic acid,
Azelaic acid, sebacic acid, maleic acid, itaconic acid,
Examples include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, citric acid, salicylic acid, pyruvic acid, malic acid and the like. Among them, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, citric acid and the like are preferable, and oxalic acid, malonic acid, citric acid and the like are more preferable in terms of a high effect of suppressing thickening. These are used alone or in combination of two or more.

The compounding amount of the compound having a carboxyl group is 0.01 to 30 parts by weight based on 100 parts by weight of the component (a).
It is preferable to use parts by weight. When the blending amount is 0.01
If the amount is less than 30 parts by weight, the effect of storage stability tends to decrease, and if it exceeds 30 parts by weight, sensitivity tends to be insufficient.

In the present invention, a dispersant may be added to the photosensitive resin composition constituting the photosensitive resin composition layer containing the phosphor (A) in order to improve the dispersion of the phosphor. Is preferred. Examples of dispersants include inorganic dispersants (silica gel, bentonite, kaolinite, talc, hectorite, montmorillonite, saponite, beidellite, etc.), and organic dispersants (aliphatic amide, aliphatic ester). Polyethylene oxide type, sulfate type anion activator, polycarboxylic acid amine salt type, polycarboxylic acid type, polyamide type, polymer polyether type, acrylic copolymer type, special silicone type, etc.). These can be used alone or in combination of two or more.

The amount of the dispersant used is not particularly limited, and is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the component (a).
It is preferably 0 parts by weight. If this usage is 0.0
If it is less than 1 part by weight, the effect of addition tends not to be exhibited,
If the amount exceeds 100 parts by weight, pattern formation accuracy (the property of obtaining a pattern formed of a photosensitive resin composition containing a phosphor, which is dimensionally accurate and desired in a desired shape after development) tends to decrease.

In the present invention, the photosensitive resin composition constituting the photosensitive resin composition layer containing the phosphor (A) is used in order to prevent the phosphor from peeling off the PDP substrate after firing. It is preferable to use a binder. Examples of the binder include a low-melting glass, a metal alkoxide, and a silane coupling agent. These are used alone or in combination of two or more.

The amount of the binder used is not particularly limited, and is 0.01 to 10 parts by weight based on 100 parts by weight of the component (d).
The amount is preferably 0 parts by weight, more preferably 0.05 to 50 parts by weight, and particularly preferably 0.1 to 30 parts by weight. If the amount is less than 0.01 part by weight, the effect of binding the phosphor tends not to be exhibited, and
If it exceeds 00 parts by weight, the luminous efficiency tends to decrease.

In the present invention, the photosensitive resin composition constituting the photosensitive resin composition layer containing the phosphor (A) includes a dye, a color former, a plasticizer, a pigment, a polymerization inhibitor, a surface modifier, Agents, stabilizers, adhesion-imparting agents, thermosetting agents, and the like can be added as necessary.

As the resin layer containing the fine particles (C) in the present invention, a layer of a mixture of the fine particles and a thermoplastic resin (B) described later is preferable.

The fine particles may be any substance that reflects and scatters light, and organic fine particles, inorganic fine particles and the like can be used.

As the organic fine particles, fine particles synthesized by a known method such as suspension polymerization, emulsion polymerization, and seed polymerization can be used. Examples of the monomer used for synthesizing the organic fine particles include (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group at a terminal, a styrene-based monomer (styrene, α-methylstyrene, pt-butylstyrene, etc.), Olefinic monomers (butadiene, isoprene, chloroprene, etc.), vinyl monomers (vinyl chloride, vinyl acetate, etc.), nitrile monomers (acrylonitrile, methacrylonitrile, etc.), 1- (methacryloyloxyethoxycarbonyl) -2- (3 '-Chloro-
2'-hydroxypropoxycarbonyl) benzene, m
-Divinylbenzene, p-divinylbenzene, urethane diacrylate compounds, trivinylbenzene and the like.

Further, a polymer comprising the above-mentioned monomer, a polyether resin, a cellulose derivative, a polyamide resin, a polyvinyl acetal resin, a polyester resin, a polycarbonate resin, polytetrafluoroethylene or aramid fiber, carbon fiber, or the like is mortar- or ball-milled.
Pulverize with a pulverizer such as a pin disk mill or jet mill,
Fine particles can be used in the same manner.

Examples of the inorganic fine particles include fine particles of glass, silica gel, alumina, silicon carbide, silicon nitride, potassium titanate, aluminum borate, and the like. Fine particles of a metal or metal oxide can also be used as inorganic fine particles. As the shape of the fine particles, spherical,
Oval spheres, flat shapes, needle shapes, and amorphous shapes are used. These fine particles are used alone or in combination of two or more.

The size of the fine particles in the present invention is preferably 0.01 μm to 100 μm in average particle size.
More preferably, the thickness is 0.05 μm to 80 μm. When the average particle size is less than 0.01 μm or more than 100 μm, the efficiency of scattering light tends to decrease. It is essential that the maximum diameter of the fine particles in the present invention is not more than the opening width (10 in FIG. 5) of the recess after forming the photosensitive resin composition layer containing the phosphor (A).
When the maximum diameter of the fine particles is larger than the opening width of the concave portion after the photosensitive resin composition layer containing the phosphor (A) is formed, the fine particles do not enter the concave portion, and the efficiency of scattering light is reduced. Tend to.

(B) The resin constituting the thermoplastic resin is not particularly limited as long as it is softened at the temperature during the heat and pressure bonding. For example, polyethylene, polypropylene, polymethylpentene, polycarbonate, polyurethane, Teflon, rubber (Butadiene rubber, styrene butadiene rubber, silicon rubber, etc.), polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride, polystyrene, polyvinyl toluene, polyacrylate, polymethacrylate, copolymer of ethylene and vinyl acetate, Copolymer of ethylene and acrylate, copolymer of vinyl chloride and vinyl acetate, copolymer of styrene and acrylate or methacrylate, copolymer of vinyltoluene and acrylate or methacrylate , Polyvinyl alcohol Coal-based resin (polyacrylate or polymethacrylate hydrolyzate, polyvinyl acetate hydrolyzate, ethylene-vinyl acetate copolymer hydrolyzate, ethylene-acrylate copolymer A hydrolyzate of a copolymer of vinyl chloride and vinyl acetate, a hydrolyzate of a copolymer of styrene and an acrylate or methacrylate,
Hydrolysates of copolymers of vinyl toluene and acrylic or methacrylic esters, etc.), water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polyvinylpyrrolidone, unsaturated carboxylic acids Examples thereof include a resin having a carboxyl group obtained by copolymerizing an acid and an unsaturated monomer copolymerizable therewith. These are used alone or in combination of two or more.

Further, (B) the thermoplastic resin can prevent color mixing,
(E) thermoplastic resin, (f)
It can also be constituted by a photosensitive resin composition containing a photopolymerizable unsaturated compound having an ethylenically unsaturated group and (g) a photoinitiator that generates free radicals upon irradiation with active light.

As the thermoplastic resin (e), (B) a resin usable as a resin constituting the thermoplastic resin and (A) a photosensitive resin constituting a photosensitive resin composition layer containing a phosphor The (a) film-imparting polymer that can be used in the composition can be used. (F) The photopolymerizable unsaturated compound having an ethylenically unsaturated group can be used in the photosensitive resin composition constituting the photosensitive resin composition layer containing the (A) phosphor described above (b) Photopolymerizable unsaturated compounds having an ethylenically unsaturated group can be used. (G) As a photoinitiator that generates free radicals upon irradiation with actinic light, it can be used in the photosensitive resin composition constituting the photosensitive resin composition layer containing the above-mentioned (A) phosphor (c). Photoinitiators that generate free radicals upon irradiation with actinic light can be used.

The compounding amount of the component (e) is 10 to 100 with the total amount of the components (e) and (f) being 100 parts by weight.
The weight is preferably set to 20 parts by weight, more preferably 20 to 80 parts by weight. When the amount is less than 10 parts by weight, when the photosensitive element is used as a photosensitive element, the photosensitive resin composition tends to exude from the end of the roll due to the flow, or the film-forming property tends to decrease.

The amount of component (f) is preferably 0 to 90 parts by weight, more preferably 20 to 80 parts by weight, based on 100 parts by weight of the total of components (e) and (f). preferable. If this amount exceeds 90 parts by weight,
In the case of a photosensitive element, there is a tendency that it exudes from the end due to the flow, or the film-forming property decreases.

The amount of the component (g) is preferably 0.01 to 30 parts by weight based on 100 parts by weight of the total of the components (e) and (f).
More preferably, the content is 0.1 to 20 parts by weight. If the amount is less than 0.01 part by weight, the sensitivity tends to be insufficient. If the amount exceeds 30 parts by weight, the active light absorption on the exposed surface increases, and the internal light curing is insufficient. Tend to be.

Further, a surface modifier and a polymerization inhibitor may be added to the thermoplastic resin (B) as required. Also,
(B) The thermoplastic resin is used in a developing step described below.
(A) a photosensitive resin composition layer containing a phosphor and (B)
The thermoplastic resin can also be developed using the same developer. Those which can be developed with the same developer include those which are soluble in water or an aqueous alkaline solution.

Examples of the resin constituting the thermoplastic resin (B) soluble in water or an aqueous alkali solution include polyvinyl alcohol-based resins (a hydrolyzate of polyacrylate or polymethacrylate, a hydrolyzate of polyvinyl acetate). Hydrolyzate of copolymer of ethylene and vinyl acetate, hydrolyzate of copolymer of ethylene and acrylic acid ester, hydrolyzate of copolymer of vinyl chloride and vinyl acetate, styrene and acrylic Hydrolysates of copolymers of acid esters or methacrylic esters, hydrolysates of copolymers of vinyl toluene with acrylic esters or methacrylic esters, etc.), water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose ethers , A water-soluble salt of carboxyalkyl starch, polyvinylpyrrolidone,
Examples include a resin having a carboxyl group obtained by copolymerizing an unsaturated carboxylic acid and an unsaturated monomer copolymerizable therewith.

Examples of the resin having a carboxyl group obtained by copolymerizing an unsaturated carboxylic acid and an unsaturated monomer copolymerizable therewith include, for example, unsaturated carboxylic acids (acrylic acid, methacrylic acid, maleic acid). , Fumaric acid, itaconic acid, etc.) and vinyl monomer (a) usable for the photosensitive resin composition constituting the photosensitive resin composition layer containing the phosphor (A), It is preferable to use a vinyl copolymer obtained by copolymerizing a monomer with a monomer.

The resin having a carboxyl group obtained by copolymerizing an unsaturated carboxylic acid and an unsaturated monomer copolymerizable therewith has a weight average molecular weight of 5,000.
~ 300,000, preferably 20,000
More preferably, it is set to １５０150,000. If the weight average molecular weight is less than 5,000, the film formability and flexibility of the photosensitive element tend to decrease, and if it exceeds 300,000, the developability tends to decrease.

Further, as a thermoplastic resin (B) which is soluble in an aqueous alkali solution, it can be developed with a developing solution.
Adjust the carboxyl group content (defined by the acid value (mgKOH / g)) of the resin having a carboxyl group obtained by copolymerizing an unsaturated carboxylic acid and an unsaturated monomer copolymerizable therewith. be able to. For example, when developing using an aqueous alkali solution such as sodium carbonate or potassium carbonate, the acid value is preferably set to 90 to 260. If the acid value is less than 90, development tends to be difficult, and if it exceeds 260, developer resistance tends to decrease. When developing using an aqueous developing solution comprising water or an aqueous alkaline solution and one or more organic solvents, the acid value is preferably from 16 to 260. When the acid value is less than 16, development tends to be difficult, and 2
If it exceeds 60, the developer resistance tends to decrease.

Further, a developer (emulsion developer) comprising water and at least one organic solvent not soluble in water,
When developing using an organic solvent development such as 1,1-trichloroethane, the polymer imparting film properties of the photosensitive resin composition may not contain a carboxyl group.

Further, in order to improve the film properties of the thermoplastic resin (B), a plasticizer may be added to the resin constituting the thermoplastic resin.

The plasticizer is represented by the general formula (III)

Embedded image (Wherein, R ⁵ represents a hydrogen atom or a methyl group, Y ¹ represents a hydrogen atom or a saturated hydrocarbon group or a polyalkylene glycol residue which may have a substituent, and Y ² represents
A hydroxyl group or a saturated hydrocarbon group or a polyalkylene glycol residue which may have a substituent;
A polyalkylene glycol such as polypropylene glycol and its derivatives, polyethylene glycol and its derivatives, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, and biphenyl. Diphenyl phosphate and the like.

The mixing ratio of the fine particles in the resin layer containing the fine particles (C) and the thermoplastic resin (B) is preferably from 1 to 500 parts by weight based on 100 parts by weight of the thermoplastic resin. It is more preferably from 400 to 400 parts by weight, particularly preferably from 3 to 300 parts by weight, particularly preferably from 4 to 200 parts by weight. If the amount of the fine particles is less than 1 part by weight, the efficiency of scattering light tends to decrease, and if it exceeds 500 parts by weight, the light transmittance tends to decrease.

Hereinafter, each step of the method for producing a phosphor pattern of the present invention will be described in detail. [(I) Step of Forming (A) Photosensitive Resin Composition Layer Containing Phosphor and (C) Resin Layer Containing Fine Particles on Substrate Having Irregularities] The step (I) in the present invention comprises: ,
(Ia) a step of (A) forming a photosensitive resin composition layer containing a phosphor on a substrate having irregularities; and (Ib) (A)
(C) forming a resin layer containing fine particles on the photosensitive resin composition layer containing the phosphor,
(I ′) A method including a step of simultaneously forming (A) a photosensitive resin composition layer containing a phosphor and (C) a resin layer containing fine particles on a substrate having irregularities is employed.

(Ia) Step of Forming (A) Phosphor-Containing Photosensitive Resin Composition Layer on Substrate Having Irregularities and (Ib) (A) Phosphor-Containing Photosensitive Resin Composition Layer (C) a step of forming a resin layer containing fine particles is described above. [(Ia) Step of Forming (A) Photosensitive Resin Composition Layer Containing Phosphor on Irregularity Substrate] FIG.
(A) The state in which the photosensitive resin composition layer 6 containing the phosphor was formed was shown. The method for forming the (A) phosphor-containing photosensitive resin composition layer on the uneven surface 5 of the uneven substrate 1 according to the present invention is not particularly limited. (A) a method of forming a photosensitive resin composition layer 6 containing a phosphor by directly applying and drying a photosensitive resin composition containing a phosphor, and (A) a photosensitive resin composition containing a phosphor And a method of forming on the uneven surface 5 using a photosensitive element having a material layer.

The method of directly applying the photosensitive resin composition containing the phosphor (A) in the form of a solution and drying it to form the photosensitive resin composition layer 6 containing the phosphor (A) may be, for example, as follows. The components constituting the (A) phosphor-containing photosensitive resin composition layer are directly applied to the uneven surface 5 as a uniformly dispersed solution by dissolving or dispersing the components in a dissolvable or dispersible solvent. And drying. In the method of direct application, (A) a solvent capable of dissolving or dispersing each component constituting the photosensitive resin composition layer containing a phosphor includes, for example, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, Ethyl cellosolve, γ-butyrolactone, N-methylpyrrolidone, dimethylformamide, tetramethylsulfone, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, chloroform,
Examples include methylene chloride, methyl alcohol, and ethyl alcohol. These are used alone or in combination of two or more.

In the direct coating method, examples of the coating method include doctor blade coating, Meyer bar coating, roll coating, screen coating, spinner coating, ink jet coating, spray coating, and the like.
Dip coating, gravure coating, curtain coating, and the like can be used.

In the coating step, the above (A)
It is preferable that the material of the coating device at a portion that comes into contact with the solution uniformly dispersed by dissolving or mixing each component constituting the layer in a solvent capable of dissolving or dispersing the component is a nonmetallic material. When the material of the contacting portion is metal, the coating device in contact with the phosphor in the solution of each component constituting the layer (A) is polished, and the polishing powder is converted into the phosphor (A). Tends to be mixed as an impurity into the solution of each component constituting the photosensitive resin composition layer containing.

In the method of direct application, drying can be carried out by using a known drying method. The drying temperature is preferably 40 to 130 ° C., and the drying time is 10 to 90 minutes. Is preferred.

The thickness of the photosensitive resin composition layer containing the phosphor (A) after drying is not particularly limited.
μm, more preferably 20 to 120 μm, and particularly preferably 30 to 80 μm. If the thickness is less than 10 μm, a phosphor pattern after firing, which will be described later, tends to be thin, and the luminous efficiency tends to decrease. If the thickness exceeds 200 μm, the phosphor pattern after firing becomes thick, and the light emission area of the phosphor screen. And the luminous efficiency tends to decrease.

In the method of forming (A) the photosensitive element having the photosensitive resin composition layer containing the phosphor on the uneven surface 5, the photosensitive element containing (A) It is necessary to produce a photosensitive element having a resin composition layer. The photosensitive element having the layer (A) is a solution in which the components constituting the layer (A) are uniformly dispersed by dissolving or mixing in a solvent capable of dissolving or dispersing. It can be obtained by drying.

In preparing a photosensitive element having the layer (A), the solvent capable of dissolving or dispersing the components constituting the layer (A) includes, for example, toluene, acetone, and the like.
Methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, γ-butyrolactone,
Examples include N-methylpyrrolidone, dimethylformamide, tetramethylsulfone, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, chloroform, methylene chloride, methyl alcohol, ethyl alcohol and the like. These are used alone or in combination of two or more.

As a support film for producing a photosensitive element having the layer (A), a support film which is chemically and thermally stable and is composed of a flexible substance, for example, polyethylene terephthalate, Polycarbonate,
Examples thereof include polyethylene and polypropylene, and among them, polyethylene terephthalate and polyethylene are preferable, and polyethylene terephthalate is more preferable. Since the support film must be removable from the layer (A) later, it must not have been subjected to a surface treatment or made of a material that cannot be removed. The thickness of the support film is preferably 5 to 100 μm, more preferably 10 to 80 μm.

As a coating method for producing the photosensitive element having the layer (A), a known method can be used, and examples thereof include a knife coating method, a roll coating method, a spray coating method, a gravure coating method, and a bar coating method. A coating method, a curtain coating method and the like can be mentioned.

In this coating step, the above (A)
It is preferable that the material of the coating device at a portion that comes into contact with the solution uniformly dispersed by dissolving or mixing each component constituting the layer in a solvent capable of dissolving or dispersing the component is a nonmetallic material. When the material of the contacting portion is a metal, the coating device in contact with the phosphor in the solution of each component constituting the layer (A) is polished by the phosphor, and the polishing powder is converted into the fluorescent material (A). It tends to be mixed as an impurity into the solution of each component constituting the photosensitive resin composition layer containing the body.

The drying temperature for preparing the photosensitive element having the layer (A) is preferably from 60 to 130 ° C., and the drying time is preferably from 3 minutes to 1 hour.

The thickness of the photosensitive resin composition layer (A) of the photosensitive element having the layer (A) is not particularly limited, but is preferably from 10 to 200 μm, preferably from 20 to 120 μm. More preferably, 30
It is particularly preferable that the thickness be set to 80 μm. This thickness is 1
If it is less than 0 μm, the phosphor pattern after firing becomes thin,
Luminous efficiency tends to decrease. If it exceeds 200 μm, the phosphor pattern after firing becomes thick, and the luminous area of the phosphor screen tends to be reduced, so that luminous efficiency tends to decrease.

The photosensitive resin composition of the photosensitive element having the layer (A) has a viscosity at 100 ° C. of 1 to 1 × 10 ⁷ P
a · sec, more preferably 2 to 1 × 10 ⁶ Pa · sec, particularly preferably ⁵ to 1 × 10 ⁵ Pa · sec, and 10 to 1 × 10 ⁴ Pa · sec. It is very preferable that When the viscosity at 100 ° C. is less than 1 Pa · sec, when the viscosity at room temperature becomes too low to form a photosensitive element, the photosensitive resin composition layer containing the phosphor (A) flows from the end by flow. It tends to exude and film formability tends to decrease. In addition, 1 × 10 ⁷ Pa ·
When the time exceeds sec, the formability of the photosensitive resin composition layer containing the phosphor (A) on the inner surface of the concave portion of the substrate having irregularities described later tends to decrease.

The sensitivity of the photosensitive resin composition layer containing the phosphor (A) in the present invention may be determined in the step of imagewise irradiating an actinic ray described later with Hitachi Chemical Co., Ltd.
(A) phosphor remaining after imagewise irradiation with actinic light at a predetermined dose of actinic radiation using a 21-step step tablet or the like and development in a step of removing unnecessary portions by development described later. Is preferably 1 to 21 steps, more preferably 1.5 to 18 steps, more preferably 2 to 21 steps in the photosensitive resin composition layer containing
It is particularly preferred to have 15 stages.

The resolution of the photosensitive resin composition layer containing the phosphor (A) in the present invention is determined by irradiating a predetermined actinic ray with a photomask for evaluating resolution, manufactured by Hitachi Chemical Co., Ltd. When the photosensitive resin composition layer containing the phosphor (A) remains after the image is irradiated with actinic rays in an amount and developed in the step of removing unnecessary portions by development described below, the minimum line / space is smaller. , Preferably 1 mm / 1 mm or less, more preferably 900 μm / 900 μm or less, and particularly preferably 800 μm / 800 μm.

The adhesion of the (A) phosphor-containing photosensitive resin composition layer of the present invention can be determined by using a photomask for adhesion evaluation manufactured by Hitachi Chemical Co., Ltd. When the actinic ray is irradiated imagewise with the irradiation amount of light and developed in the step of removing unnecessary portions by development described later, the remaining line (A) of the minimum line of the photosensitive resin composition layer containing the phosphor is reduced. Space is 400μm / 400μ
m, preferably 350 μm / 400 μm
And more preferably 300 μm / 400 μm
m is particularly preferred.

On the photosensitive element having the photosensitive resin composition layer containing the phosphor (A) thus obtained, a peelable cover film can be further laminated. As the cover film, polyethylene,
Examples thereof include polypropylene, polyethylene terephthalate, and polycarbonate. The adhesive strength between the cover film and the layer (A) is preferably smaller than the adhesive strength between the support film and the layer (A). The thickness of the cover film is not particularly limited, but is preferably 5 to 100 μm, and particularly preferably 10 to 90 μm. The photosensitive element having the layer (A) thus obtained can be stored in a roll shape.

(A) As a method of forming the (A) layer on the uneven surface 5 using a photosensitive element having a photosensitive resin composition layer containing a phosphor, for example, the method of forming the (A) layer A method of laminating the layer (A) of the photosensitive element on a substrate having irregularities and embedding the layer (A) in the inner surface of the concave portion by heating, pressure bonding, etc. (A) A method of burying the layer is exemplified.

As a method of laminating the (A) layer of the photosensitive element having the (A) layer on a substrate having irregularities and embedding the (A) layer in the inner surface of the concave portion by heating, pressure bonding, or the like, for example, When a cover film is present on the photosensitive element having the layer (A), a method of removing the cover film and then heat-pressing the layer so that the layer (A) is in contact with the substrate having irregularities may be used. .

The heating temperature during thermocompression bonding is 10 to 130 ° C.
The temperature is preferably set to 20 to 120 ° C, more preferably 30 to 110 ° C. If the heating temperature is lower than 10 ° C., the layer (A) tends to be unable to adhere sufficiently to a substrate having irregularities.
When the temperature exceeds 30 ° C., the layer (A) tends to be thermally cured.

The compression pressure at the time of heat compression is 1 × 10 ² to 1 × 10 ⁷ Pa, which is a gauge pressure (normal pressure 1 atm is 0).
It is more preferably 5 × 10 ^{2 to} 5 × 10 ⁶ Pa, and particularly preferably 1 × 10 ⁴ to 4 × 10 ⁶ Pa. When the pressure is less than 1 × 10 ² Pa, the layer (A) tends to be unable to sufficiently adhere to the substrate having irregularities, and when it exceeds 1 × 10 ⁷ Pa, the barrier ribs of the substrate having irregularities are broken. Tend to be.

Since the above pressure is the cylinder pressure of the laminator, which is a pressure bonding device, it is preferable to convert the pressure into a linear pressure of 2.4 to 2.4 × 10 ⁵ N / m.
It is more preferably set to 2 to 1.2 × 10 ⁵ N / m.
It is particularly preferred to be 4 × 10 ^{2 to} 2.4 × 10 ⁴ N / m. If the pressure is less than 2.4 N / m, the (A) layer 6
When the PDP substrate exceeds 2.4 × 10 ⁵ N / m, the barrier rib of the PDP substrate tends to be broken.

Here, as a method of setting the linear pressure to 5 × 10 ³ N / m, for example, a laminator having a cylinder diameter of 40 mmφ is used, and a substrate having a thickness of 3 mm and a length of 10 cm × width of 10 cm (square) is used. , Laminator cylinder pressure (normal pressure 1 atm is 0
) Is set to 2 kgf / cm ² so that the linear pressure is 5 ×
10 ³ N / m method, using a laminator with a cylinder diameter of 40 mmφ, thickness 3 mm, length 20 cm x width 20 cm (square)
Of the laminator cylinder pressure (normal pressure 1 atm)
Is 4 kgf / cm ² to obtain a linear pressure of 5 × 10 ³ N / m.

If the photosensitive element having the layer (A) is heated as described above, it is not necessary to pre-heat the PDP substrate on which the barrier ribs are formed, but the embedding property of the layer (A) in the inner surface of the concave portion is not necessary. In order to further improve the above, it is preferable to perform a pre-heat treatment on the substrate having the irregularities. Furthermore, for the same purpose, the above-mentioned operations of the press bonding and the heat pressing can be performed under reduced pressure of 5 × 10 ⁴ Pa or less.

Further, from the viewpoint of further improving the embedding property of the layer (A) into the inner surface of the concave portion, the surface of the pressure roll is preferably
A highly flexible material such as rubber or plastic can also be used. Note that the thickness of the layer made of a material having high flexibility is preferably 200 to 400 μm. Further, in order to further improve the embedding property of the layer (A) into the inner surface of the concave portion, the layers can be laminated while heating the photosensitive elements with a heating roll or the like. After the completion of the lamination in this manner, 1 to 12 at a temperature of 30 to 150 ° C.
Heating can be performed for 0 minutes. At this time, the support film can be removed as necessary.

[(Ib) Step of Forming (C) Resin Layer Containing Fine Particles on Photosensitive Resin Composition Layer Containing (A) Phosphor] (A) Photosensitive Resin Composition Containing Phosphor FIG. 4I shows a state in which a resin layer containing fine particles (C) is formed on the material layer. The method for forming the resin layer containing fine particles (C) on the photosensitive resin composition layer containing phosphor (A) formed in the step (Ia) is not particularly limited. A) a method in which a resin layer containing fine particles is formed by directly applying and drying the layer (A) on the layer (A) formed in the step (c), and using a film having a resin layer containing fine particles (C) Then, a method of forming on the (A) layer formed by the step (Ia) and the like can be mentioned.

The method of directly applying and drying on the (A) phosphor-containing photosensitive resin composition layer formed in the step (Ia) described above is, for example, the method described in (C) above. A) A solution in which each component constituting the resin layer containing fine particles is uniformly dispersed by dissolving or dispersing in a solvent capable of dissolving or dispersing is formed on the layer (A) formed by the step (Ia). For example, a method of directly applying the composition to a substrate, followed by drying.

Examples of the solvent capable of dissolving or dispersing the components constituting the resin layer containing the fine particles (C) include water, toluene, acetone, methyl ethyl ketone, and the like.
Examples thereof include methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, γ-butyrolactone, N-methylpyrrolidone, dimethylformamide, tetramethyl sulfone, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, chloroform, methylene chloride, methyl alcohol, and ethyl alcohol. These are used alone or in combination of two or more.

The solution constituting the resin layer containing the fine particles (C) is directly applied on the photosensitive resin composition layer containing the phosphor (A) formed in the step (Ia), and dried. The coating method and drying conditions when forming by
The step (Ia) can be performed in the same manner as in the step (A) of forming the photosensitive resin composition layer containing the phosphor.

Further, a layer (C) composed of a plurality of layers can be formed by applying a solution constituting a resin layer containing different (C) fine particles repeatedly. When the layer (C) composed of a plurality of layers is formed, it is sufficient that at least one of the plurality of layers contains fine particles, and the other layers do not necessarily need to contain fine particles.

Further, the components constituting the resin layer containing the fine particles (C) are mixed to form a film,
In the method for forming the resin layer containing fine particles on the (A) layer formed by the step (Ia) by using this, the (C) resin layer containing fine particles may be formed into a film shape as follows:
A uniform fine particle dispersion solution is obtained by dissolving or mixing each component constituting the layer (C) in a solvent that dissolves the components, and a knife coat method, a roll coat method, a spray coat method, a gravure coat method is formed on the support film. Using a known coating method such as a bar coating method and a curtain coating method,
It can be formed into a film by coating and drying.

In the case where the resin layer containing the fine particles (C) is formed into a film, the solution constituting the resin layer containing the different fine particles (C) may be formed of a plurality of layers by repeatedly applying the solution. C) It can also be formed into a film having a layer. When the layer (C) composed of a plurality of layers is formed, it is sufficient that at least one of the plurality of layers contains fine particles, and the other layers do not necessarily need to contain fine particles.

(C) The thickness of the resin layer containing fine particles is as follows:
Although there is no particular limitation, the thickness is preferably 10 to 200 μm, more preferably 20 to 100 μm, from the viewpoint of the embedding property of the substrate having the unevenness into the inner surface of the recess.

(C) The thermoplastic resin (B) used for the resin layer containing fine particles has a viscosity at 100 ° C. of 1 to 1 ×.
10 ⁷ Pa · sec, preferably 2 to 1 × 10 ⁶ Pa · s
It is more preferably set to ec, particularly preferably set to ⁵ to 1 × 10 ⁵ Pa · sec, and particularly preferably set to 10 to 1 × 10 ⁴ Pa · sec. The viscosity at 100 ° C is 1 Pa
If the viscosity is less than sec, when the viscosity at room temperature becomes too low to form a film, the thermoplastic resin (B) tends to bleed out from the end due to the flow, and the film formability tends to decrease. On the other hand, if it exceeds 1 × 10 ⁷ Pa · sec, the formability of the (A) phosphor-containing photosensitive resin composition layer on the inner surface of the concave portion of the substrate having irregularities described later tends to decrease.

Further, a releasable cover film can be further laminated on the resin layer containing the fine particles (C). Examples of the cover film include polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, and the like. The cover film and the resin layer containing the fine particles (C) are less than the adhesive force between the support film and the resin layer containing the fine particles (C). It is preferable that the adhesive strength is smaller. The thickness of the cover film is not particularly limited, but is preferably 5 to 100 μm,
More preferably, it is 90 μm.

The resin layer containing the fine particles (C) thus formed into a film can be stored in a roll.

(C) The resin layer containing fine particles is
Examples of a method for forming a layer (A) in a good buried state on the inner surface of a substrate having irregularities by using the resin composition layer containing a phosphor as a burying layer for firmly burying the layer in the substrate include, for example, On a substrate having irregularities, a photosensitive resin composition layer containing the phosphor (A) of the photosensitive element is formed, and a layer (C) is disposed thereon.
A method in which the buried layer is heated and pressed is exemplified.

On a substrate having irregularities, the (A) layer of the photosensitive element having the (A) resin composition layer containing a phosphor is formed, and (C) a resin containing fine particles is formed thereon. As a method of heating and pressing the layer (C) in a state where the layers are arranged, for example, after the layer (A) of the photosensitive element having the layer (A) is formed, the layer (A) is formed on the layer (A). If a support film is present, after removing the support film, a resin layer containing fine particles (C) (if a cover film is present, the cover (After the film is removed), and heat-pressing with a heating roll or the like.

At this time, an intermediate layer made of polyethylene, polypropylene, polycarbonate, polytetrafluoroethylene, polyethylene terephthalate, or the like is arranged between the layer (A) and the layer (C), and is heated and pressed by a heating roll or the like. Is also good. The intermediate layer may be a single layer or a stack of two or more layers.

The heating temperature during thermocompression bonding is 10 to 130 ° C.
The temperature is preferably set to 20 to 120 ° C, more preferably 30 to 110 ° C. If the heating temperature is lower than 10 ° C., the embedding property of the substrate having the unevenness of the layer (A) into the inner surface of the concave portion tends to decrease, and if the heating temperature exceeds 130 ° C., the layer (A) tends to thermoset. .

[0098] The compression pressure at the time of heat compression is 1 × 10 ⁴ to 1 × 10 ⁷ Pa in gauge thickness (normal pressure 1 atm is 0).
The pressure is preferably set to 2 × 10 ^{4 to} 5 × 10 ⁶ Pa, more preferably 4 × 10 ⁴ to 1 × 10 ⁶ Pa. The crimping pressure is 1 in × less than 10 ⁴ Pa, there is a tendency to decrease the embedding of the recess inner surface of the substrate having unevenness of layer (A), when more than 1 × 10 ⁷ Pa, the substrate having an uneven Irregularities (such as barrier ribs) tend to be destroyed.

[0099] Since the pressing pressure at the time of heating and pressing is the cylinder pressure of the laminator, it is preferable to convert the pressure into a linear pressure of 2.4 × 10 ^{2 to} 2.4 × 10 ⁵ N / m. 4.8 × 10 ^{2 to} 1.2 × 10 ⁵ N / m, more preferably 9.6 × 10 ^{2 to} 2.4 × 10 ⁴ N / m. This pressure is 2.4 × 10 ² N
If it is less than / m, the embedding property of the (A) layer 6 into the space of the PDP substrate tends to decrease, and if it exceeds 2.4 × 10 ⁵ N / m, the barrier rib of the PDP substrate tends to be broken. is there.

(C) If the resin layer containing the fine particles is heated as described above, it is not necessary to pre-heat the substrate having the irregularities on which the (A) layer is laminated, but the inner surface of the concave portion of the (A) layer is not necessary. (A)
It is preferable that the substrate having the unevenness in which the layers are stacked be preheat-treated. The preheating temperature at this time is preferably 30 to 130 ° C., and the preheating time is preferably 0.5 to 20 minutes.

In order to further improve the embedding property of the layer (A) into the inner surface of the concave portion, the surface of the pressure roll is preferably
A highly flexible material such as rubber or plastic can also be used. Note that the thickness of the layer made of a material having high flexibility is preferably 200 to 400 μm. Further, for the same purpose, under the reduced pressure of 5 × 10 ⁴ Pa or less, it is also possible to perform the operation of the above-mentioned pressure bonding and heat pressure bonding, and, after lamination is completed, in the range of 30 to 150 ° C, 1 to 1
Heating for 120 minutes is also possible. At this time, if a support film exists on the layer (C), the support film may be removed as necessary.

Further, (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group in the (A) layer or (c) a photoinitiator which generates free radicals upon irradiation with active light migrates to the (C) layer. If you are prone to
In order to suppress this phenomenon, after lamination is completed, the substrate having irregularities can be cooled (usually in the range of −50 to 50 ° C.).

The step (I) in the present invention comprises:
It can also be carried out by a method comprising simultaneously forming (A ') a photosensitive resin composition layer containing a phosphor and (C) a resin layer containing fine particles on a substrate having irregularities. [(I ') Step of simultaneously forming (A) a photosensitive resin composition layer containing a phosphor and (C) a resin layer containing fine particles on a substrate having irregularities] (A) layer and (C) ) Layer is formed at the same time as the photosensitive element having the above-mentioned (A) layer and the above-mentioned (C) layer.
A method of laminating two layers simultaneously (when there is an intermediate layer, three or more layers at the same time) by using a film having a layer so that the layer (A) is in contact with the surface of the substrate having irregularities is mentioned. Can be The conditions for the thermocompression bonding of the layer (C) can be used as the thermocompression bonding conditions when the two layers are laminated while being thermocompression bonded simultaneously.

As a method for simultaneously forming the layer (A) and the layer (C), (I ″)
A photosensitive element for forming a phosphor pattern, comprising a resin layer containing fine particles and having thereon a (A) photosensitive resin composition layer containing a phosphor, is provided on a substrate having irregularities. (A) The layers are laminated so that the layers are in contact with each other.
A method of laminating two layers simultaneously (or three or more layers at the same time when there is an intermediate layer) on the substrate having the layer and the (C) layer having irregularities by heating and laminating the layers.

[(I ″) Fluorescence comprising (C) a resin layer containing fine particles on a support film, and (A) a photosensitive resin composition layer containing a phosphor thereon Stacking a photosensitive element for forming a body pattern on a substrate having irregularities such that the layer (A) is in contact with the substrate, and simultaneously forming the layers (A) and (C) on the substrate having irregularities In the step (I ″), a photosensitive element for forming a phosphor pattern, in which the resin layer containing fine particles (C) and the photosensitive resin composition layer containing phosphor (A) are integrated, is prepared. There is a need to. The photosensitive element for forming a phosphor pattern in which the layer (C) and the layer (A) are integrated is formed by forming the layer (A) on a support film in the same manner as described above, and then (A) A method of forming the layer (C) on the layer in the same manner as described above, and a method of separately forming the layer (A) and the layer (C) in the same manner as described above, and covering each film with the cover. If film is present,
After peeling the cover film, the (A) layer and (C)
It can be obtained by a method of laminating layers and the like.

The thermocompression bonding conditions when using the photosensitive element for forming a phosphor pattern in which the layer (C) and the layer (A) are integrated are as follows: Can be used.

In this manner, (A) the photosensitive resin composition layer containing the phosphor is uniformly formed on the inner surface of the concave portion of the substrate having irregularities, and (C) the resin layer containing fine particles is formed thereon. can do.

Hereinafter, the method for manufacturing the phosphor pattern of the present invention will be described in detail with reference to FIG. FIG. 4 is a schematic view showing an example of each step of the method for producing a phosphor pattern of the present invention. (A) Photosensitive resin composition layer 6 containing phosphor and (C) resin layer 8 containing fine particles are formed on the uneven surface of PDP substrate 1 (substrate having unevenness) on which barrier ribs 2 are formed. FIG. 4I shows the state after the completion of the step (I).

[(II) Step of irradiating actinic ray imagewise to resin layer containing fine particles (C) and photosensitive resin composition layer containing fluorescent material (A)] (II) Fine particles of (C) FIG. 4 (II) shows the state of the step of irradiating actinic rays 9 imagewise through the photomask 7 to the containing resin layer 8 and the photosensitive resin composition layer 6 containing the phosphor (A). As the photomask 7 in this step, a photomask having an active light transmission width wider than the opening width of the concave portion and a narrower active light transmission width can be used. FIG. 5 shows the opening width 10 of the concave portion and the width 11 of the barrier rib in this step. FIG. 6 is a schematic view showing the portion 12 to be light-cured.

The active light transmission width in this step is a width obtained by adding the width 11 of the left and right barrier ribs to the opening width 10 of the concave portion (when the barrier rib width 11 is 70 μm, the width is 140 μm wider than the opening width 10 of the concave portion). 1 from the opening width of the recess 10
Preferably, the width is 20 μm narrower, and the opening width of the concave portion is 1 μm.
0 plus 50% of the width 11 of the left and right barrier ribs (when the width 11 of the barrier rib is 70 μm, the opening width of the recess 10
70 μm wider than width) to 100 μm than recess opening width 10
The width is more preferably narrow, and particularly preferably 1 μm to 90 μm narrower than the opening width 10 of the concave portion.

When the width of the active light beam is larger than the width obtained by adding the width 11 of the left and right barrier ribs to the opening width 10 of the concave portion,
There is a tendency for the photocuring to proceed to the concave portion other than the inner surface of the concave portion to be photocured, and an unnecessary portion tends to remain after the development described later. If the opening width of the concave portion is more than 120 μm, the photocuring of the photosensitive resin composition layer 6 containing the phosphor (A) formed on the inner surface of the concave portion tends to be insufficient. In the subsequent development, the development resistance of the (A) layer 6 formed on the inner surface of the concave portion (the property of the remaining pattern that is not removed by the development and is not affected by the development) tends to decrease. In addition, a necessary portion of the (A) layer 6 tends to be removed.

Here, the actinic ray transmission width of the recess opening width 10 means that the recess opening width 10 is 150 μm and the barrier rib width 1
1 shows the active light beam transmission width when 70 μm. Therefore, when the size of the recess opening width 10 varies,
According to this variation rate, the range of the active light beam transmission width narrower than the recess opening width 10 is determined.

In order to further increase the light scattering efficiency, light exposure can be performed using a light scattering material sheet between the light source and the photomask 7. As the light scattering material sheet, any material can be used as long as it can refract or scatter the active light. Specific examples of the light-scattering material sheet include a quilted film having an uneven surface, an embossed film, a sand mat film, a frosted glass, a patterned glass, and a film or glass that transmits general-purpose actinic rays. Polished with a vapor or the like to form a cloudy glass, a film or glass that transmits general-purpose actinic rays is polished with a laser or the like, and a cloudy glass is formed, and the glass is treated with hydrogen fluoride or the like, and the surface is polished. And a film containing fine particles and applied so that light is scattered. These may be used alone, or two or more sheets may be used in an overlapping manner.

The light-scattering material sheet has only one surface subjected to light-scattering treatment, the both surfaces subjected to light-scattering treatment, the one having front and back surfaces subjected to light-scattering treatment, and the one having the inside subjected to light-scattering treatment. , Those in which only the inside and one side are light-scattered, those in which the inside and both sides are light-scattered,
Any of those in which the inside, front and back surfaces are subjected to light scattering treatment, and the like can be used. An active ray can be irradiated from both the front and back surfaces of a substrate subjected to light scattering treatment on only one side, and a substrate subjected to light scattering treatment having different front and back surfaces.

The light transmission amount of the light scattering material sheet was 230 nm.
It is preferably one that transmits 3 to 100% in comparison with the case where the light scattering material sheet is not used in the wavelength range of ~ 450 nm.
More preferably, it transmits 0 to 100%, and 30 to 10%.
Those that transmit 0% are more preferable, and those that transmit 50 to 100% are most preferable. When the light transmission amount of the light scattering material sheet is less than 3%, the exposure time becomes relatively long, and the working efficiency tends to decrease. The thickness of the light-scattering material sheet is 3 to 1 as compared with the case where the light-scattering material sheet is not used in a wavelength range of 230 nm to 450 nm.
Any thickness can be used as long as it can transmit 00%. The light scattering material sheet can be used at any height as long as it is between the resin layer 8 containing fine particles (C) and the active light source 9.

In FIG. 4 (II), the method of irradiating actinic rays 9 imagewise includes, for example, (A) the photosensitive resin composition layer 6 containing the phosphor in the state of FIG. C) On the resin layer 8 containing fine particles, a negative film,
A method of irradiating actinic rays 9 imagewise through a photomask 7 such as a negative glass, a positive film, a positive glass or the like can be used.

As the actinic ray 9 in this step, a known actinic light source can be used, and examples thereof include light generated from a carbon arc, a mercury vapor arc, a xenon arc, and the like.

Since the sensitivity of the photoinitiator is usually maximal in the ultraviolet region, the active light source in that case should be one that effectively emits ultraviolet light. When the photoinitiator is sensitive to visible light, for example, 9,10-phenanthrenequinone or the like, visible light is used as the active light 9 and the light source is as described above. Other than the above, a flood light bulb for photography, a sun lamp and the like can be used. In addition, as the active light beam 9 in the present invention, a parallel light beam, a scattered light beam and the like can be mentioned, and any of a parallel light beam and a scattered light beam may be used, or both may be used in one step, and both may be used in one step. It may be used separately in two stages. If both are used separately in two stages, either may be performed first.

[0119] The irradiation of active light 9 in the present step is not particularly limited, preferably in the 5~10000mJ / cm ^2, more preferably to 7~8000mJ / cm ^2, 10~5000mJ / cm ² is particularly preferred. When the irradiation amount of the actinic ray 9 is less than 5 mJ / cm ^{2, the} photocuring of the photosensitive resin composition layer 6 containing the phosphor (A) formed on the inner surface of the concave portion tends to be insufficient, which will be described later. In the development, the developer resistance of the layer (A) 6 formed on the inner surface of the concave portion (the property that the remaining pattern which is not removed by the development and is not affected by the development) tends to be reduced. On the other hand, when the dose of the actinic ray 9 exceeds 10,000 mJ / cm ² , photocuring tends to occur to portions other than the inner surface of the concave portion to be photocured, and unnecessary portions tend to remain after development described later.

[(III) Step of forming a pattern by removing the resin layer containing fine particles (C) and selectively removing the photosensitive resin composition layer containing the phosphor (A) by development] FIG. 4 (III) shows a state where unnecessary portions have been removed by the method. In FIG. 4 (III), reference numeral 6 'denotes a photosensitive resin composition layer containing the phosphor (A) after photocuring.

As a method for removing the resin layer containing the fine particles (C) in this step, for example, a pressure-sensitive adhesive tape may be adhered to the support film, or a hook-shaped jig or the like may be used to physically remove the resin layer. A method of peeling off the support film and the layer (C) (and the intermediate layer if an intermediate layer is present) from the photosensitive resin composition layer containing the phosphor (A) can be used. Further, as a method of removing the layer (C), the support film and the layer (C) (and, if an intermediate layer is present, an intermediate layer, A method of peeling off the layer can also be used.
Immediately after the support film and the layer (C) (and the intermediate layer, if present, the intermediate layer) are peeled off, the support film and the (C) are peeled off using a take-up roll or the like. It is also possible to wind up the layer (and, if present, also the intermediate layer).

As a developing method for selectively removing the (A) phosphor-containing photosensitive resin composition layer by the development in this step, for example, after the state shown in FIG. When the support film is present on the containing resin layer, the support film and the layer (C) (and the intermediate layer if an intermediate layer is present) are peeled off from the layer (A). Using a known developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent, performing development by a known method such as spraying, rocking immersion, brushing, or scrubbing, and removing unnecessary portions of the (A) layer. After the state of 4 (II), if a support film is present on the resin layer containing the fine particles (C), after removing the support film,
Using a known developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent, development is performed by a known method such as spraying, rocking immersion, brushing, or scrubbing, and unnecessary portions of the (C) layer and the (A) layer are removed. A removal method and the like can be mentioned.

As a method for removing unnecessary portions of the (C) layer and the (A) layer, water, an alkali aqueous solution, a semi-solvent aqueous solution, a semi-solvent alkaline aqueous solution, an organic solvent or the like which does not dissolve the (A) layer 6 is used. (C) After removing the layer 8 by dissolution,
Unnecessary portions of the (A) layer 6 may be removed using a developer,
When the unnecessary portion of the (A) layer 6 and the (C) layer 8 can be developed using the same developer, the unnecessary portion of the (A) layer 6 and ( C) The unnecessary portion of the layer 8 can be removed in one step. As a method for removing the (A) layer 6 and the (C) layer 8, a dry development is used.
Each can be performed alone or in one step.

In the step (III) of the present invention, (A) the photosensitive resin composition layer 6 containing the phosphor and (C) other than the inner surface of the concave portion formed in the step (II). The resin layer 8 containing the fine particles is an unnecessary portion, which needs to be removed by development. The developing time and the developing temperature at this time can be appropriately adjusted so that unnecessary portions can be removed.

The development time was determined as follows: (A) the minimum development time of the photosensitive resin composition layer 6 containing the phosphor ((A) after embedding the layer in the inner surface of the concave portion of the substrate for PDP, The time is preferably 1 to 10 times the shortest time to be removed), and the developing temperature is preferably 10 to 60 ° C. If the developing time is shorter than the minimum developing time, the undeveloped portion tends to occur. If the developing time exceeds 10 times the minimum developing time, a necessary portion of the (A) layer 6 tends to be removed. If the developing temperature is lower than 10 ° C., the developability tends to decrease, and if it exceeds 60 ° C., the developer resistance tends to decrease.

Examples of the base of the aqueous alkali solution used for development include alkali hydroxides (such as hydroxides of lithium, sodium or potassium), alkali carbonates (such as carbonates or bicarbonates of lithium, sodium or potassium), and alkalis. Metal phosphates (such as potassium phosphate and sodium phosphate), alkali metal pyrophosphates (such as sodium pyrophosphate and potassium pyrophosphate), tetramethylammonium hydroxide, triethanolamine and the like, among which sodium carbonate, Preferred are tetramethylammonium hydroxide and the like. The pH of the aqueous alkali solution used for development is preferably 9 to 11, and the temperature is set at (A) the photosensitive resin composition layer 6 containing a phosphor and (C) the resin containing fine particles. It can be adjusted according to the developability of the layer 8. Further, a surfactant, an antifoaming agent, and a small amount of an organic solvent for accelerating the development can be mixed in the alkaline aqueous solution.

Examples of the aqueous developer include those comprising water or an aqueous alkali solution and at least one organic solvent.
Here, as the base of the alkaline aqueous solution, in addition to the above substances, for example, borax, sodium metasilicate, ethanolamine, ethylenediamine, diethylenetriamine,
2-amino-2-hydroxymethyl-1,3-propanediol, 1,3-diaminopropanol-2-morpholine and the like. The pH of the aqueous developer is preferably from 8 to 12, more preferably from 9 to 10.

Examples of the organic solvent include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and the like. Is mentioned. These are used alone or in combination of two or more.

An aqueous developer comprising water and one or more organic solvents (emulsion solution when the organic solvent is not soluble in water). Examples of the organic solvent include acetone alcohol, acetone, ethyl acetate, and C 1 -C. Alkoxyethanol having 4 alkoxy groups, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, dipropylene glycol monopropyl ether, 3
-Methyl-3-methoxybutyl acrylate, 1,1,
1-trichloroethane, N-methylpyrrolidone, N, N
-Dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ-butyrolactone and the like.
These are used alone or in combination of two or more. The concentration of the organic solvent is usually in the range of 2 to 90% by weight, and the temperature can be adjusted according to the developability.

Further, a small amount of a surfactant, an antifoaming agent or the like can be mixed in the aqueous developer.

Examples of the organic solvent developer used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. Water may be added to these organic solvents in the range of 1 to 20% by weight to prevent ignition.

Known developers such as water, an aqueous alkali solution, an aqueous developer (composed of water and one or more organic solvents or an aqueous alkali solution and one or more organic solvents), and organic solvents include: From the viewpoint of preventing the phosphor from deteriorating at the time of development, it is preferable that no metal ions other than alkali metal ions or halogen ions are contained.

For the purpose of preventing the deterioration of the developing solution and the phosphor, the base of the aqueous alkali solution remaining in the photosensitive resin composition layer 6 'containing the phosphor (A) after the photocuring is replaced with an organic acid or an organic acid. Spray using inorganic acids or aqueous solutions of these acids,
Acid treatment (neutralization treatment) can be performed by a known method such as rocking immersion, brushing, and scrubbing. Examples of the acid include organic acids and inorganic acids such as saturated fatty acids, unsaturated fatty acids, aliphatic dibasic acids, aromatic dibasic acids, aliphatic tribasic acids, and aromatic tribasic acids.

Specific organic acids include, for example, formic acid,
Acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, propionic acid, capric acid, undecanoic acid, lauric acid,
Tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, palmito oleic acid, oleic acid,
Elaidic acid, linolenic acid, linoleic acid, oxalic acid, malonic acid, methyl malonic acid, ethyl malonic acid, monomethyl malonate, monoethyl malonate, succinic acid, methyl succinic acid, adipic acid, methyl adipic acid, pimelic acid, suberic acid , Azelaic acid, sebacic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, citric acid, salicylic acid, pyruvic acid, malic acid and the like. Of these, formic acid, oxalic acid, malonic acid, citric acid and the like are preferred because of their high neutralization effect.

The pH of the aqueous acid solution used for the acid treatment is preferably 2 to 6. The pH and temperature of the aqueous acid solution are controlled by adjusting the pH and temperature of the photosensitive resin composition layer 6 'containing the phosphor after photocuring.
It can be adjusted in accordance with the acid resistance (durability that does not deteriorate with acid) of the DP substrate (substrate having irregularities).
Further, after the acid treatment (neutralization treatment), a step of washing with water can be performed.

In this way, the photosensitive resin composition layer (unnecessary part) containing the phosphor (A) formed other than on the inner surface of the concave portion is removed by development, and the inner surface of the concave portion (A) after photo-curing is removed. 5) Photosensitive resin composition layer 6 ′ containing phosphor
(When the (C) layer 8 having photosensitivity is present on the (A) layer 6, a photocured (C) resin layer containing fine particles is also included).

When the photomask 7 having an opening width larger than the opening width of the concave portion is used in the above-mentioned step (II), the light-irradiated portion of the (A) layer 6 formed other than on the inner surface of the concave portion is formed. By performing this step (step (III)),
There is a tendency to be in the state shown in FIG. In this case, the photosensitive resin composition layer 6 '(unnecessary portion) containing the phosphor after photocuring (A) remaining on the inner surface of the concave portion can be completely removed by polishing or the like.

FIG. 7 is a schematic diagram showing a state after the step (III) when the photomask 7 having an opening width larger than the opening width of the concave portion is used in the step (II) of the present invention. In FIG. 7, reference numeral 13 denotes an unnecessary portion (a portion completely removed by polishing or the like). When an adhesive tape is used for the unnecessary portion instead of the polishing, the adhesive tape can be peeled off and only the unnecessary portion can be physically removed.

Further, assuming such a case, after forming a multicolor pattern composed of a photosensitive resin composition layer containing a phosphor that emits red, green, and blue, which will be described later, and before a firing step described later, In the upper part of the convex portion, a black inorganic material paste including a black inorganic pigment such as iron oxide, acid value chromium, and acid value copper and a low melting point glass frit or the like is applied or printed, or using a black inorganic material-containing photosensitive element. After forming the black stripes, baking described later can be performed.

Further, after the development, ultraviolet irradiation or heating using a high-pressure mercury lamp or the like may be performed for the purpose of improving the adhesion and chemical resistance of the phosphor-containing photoresist on the inner surface of the concave portion on the PDP substrate. The irradiation amount of the ultraviolet ray at this time is usually 0.2 to 10 J / cm ² , and heating can be performed during the irradiation. The heating temperature is 60 to 1
The temperature is preferably set to 80 ° C, more preferably 100 to 180 ° C. Further, the heating time is preferably set to 15 to 90 minutes. Irradiation and heating of these ultraviolet rays may be performed separately from irradiation and heating, and either may be performed first.

[(IV) Step of Removing Organic Components by Firing] FIG. 4 (IV) shows a state in which the phosphor pattern has been formed after removing the organic components by firing. FIG. 4 (I
In V), 12 is a phosphor pattern.

In this step, the firing method is not particularly limited, and a known firing method can be used to remove organic components other than the phosphor and the binder, thereby forming a phosphor pattern. The firing temperature at this time is 350 to 800
C., preferably 400 to 600C. The firing time is preferably from 3 to 120 minutes, more preferably from 5 to 90 minutes. The heating rate at this time is preferably 0.5 to 50 ° C./min, more preferably 1 to 45 ° C./min. In addition, 350-45 before reaching the maximum firing temperature
A step of maintaining the temperature between 0 ° C. can be provided, and the holding time is preferably 5 to 100 minutes.

In the method of manufacturing a phosphor pattern according to the present invention, the steps (I) to (III) of the present invention are repeated for each color to reduce red, green and After forming a multicolor pattern composed of a photosensitive tree composition layer containing a phosphor that emits blue light, it is preferable to perform the step (IV) to form a multicolor phosphor pattern.

In the present invention, the photosensitive resin composition layer 6 containing the phosphor (A), which contains each of the phosphors that emit red, green, and blue independently, has the following characteristics for each of the red, green, and blue colors. It can be performed in any order.

Each of the steps (I) to (III) in the present invention is repeated for each color, so that the phosphor containing the photosensitive resin composition layer containing the phosphor (A) that emits red, green and blue colors is obtained. FIG. 8 shows a state where the pattern is formed. In FIG. 8, 6'a is a first color pattern, 6'b is a second color pattern, and 6'c is a third color pattern.

FIG. 9 shows a state in which a multicolor phosphor pattern is formed. 14a is a first phosphor pattern, 14b is a second phosphor pattern, and 14c is a third phosphor pattern. .

Further, the method for producing a phosphor pattern of the present invention comprises:
From the viewpoint of suppression of film thinning and the like, (I) to (I) in the present invention.
It is preferable that the steps (IV) are repeated for each color to form a multicolor phosphor pattern that emits red, green and blue.

The back plate for a plasma display panel of the present invention is provided with the fluorescent pattern of the present invention obtained as described above on a substrate for a plasma display panel. The size of the back plate for a plasma display panel of the present invention is not particularly limited, but is 2
A size of 5 inches or more is preferable, a size of 30 inches or more diagonally is more preferable, and a size of 35 inches or more diagonally is particularly preferable.

Hereinafter, a back plate for a plasma display panel will be described with reference to FIG. Note that FIG.
11 is a schematic view showing an example of a plasma display panel (PDP). In FIG. 11, 1 is a substrate, 2 is a barrier rib, 4 is a striped discharge space, 14 is a phosphor pattern, 16 is an address electrode, 17 is a protective film, 18 is a dielectric layer, 19 is a display electrode, and 20 is a front plate substrate.

In FIG. 11, a substrate 1, barrier ribs 2,
The lower part including the phosphor pattern 14 and the address electrode 16 is the back panel for PDP, and the upper part including the protective film 17, the dielectric layer 18, the display electrode 19 and the front panel substrate 20 is the PDP.
It is a front plate for use. PDP is based on the AC voltage application method.
(AC) type PDP, DC (direct current) type PDP, etc., and the schematic diagram of FIG. 11 shown as an example is an AC type PDP.
It is. The method for producing the photosensitive element and the phosphor pattern according to the present invention comprises a cathode ray tube (CRT),
The present invention can be applied to a self-luminous display such as a field emission display (FED) and an electroluminescence display (ELD).

[0151]

The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

Production Example 1 [Preparation of Film-Promoting Polymer (a)] A flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer was charged with the components shown in Table 1 and placed under a nitrogen gas atmosphere. 80 ℃
And maintaining the reaction temperature at 80 ° C ± 2 ° C, Table 1
Was dropped uniformly over 4 hours. After dripping,
Stirring is continued at 80 ° C. ± 2 ° C. for 6 hours, and the weight average molecular weight is 8
A polymer (a) having a film property of 0000 and an acid value of 130 mgKOH / g was obtained.

[0153]

[Table 1]

Production Example 2 [(A) Production of photosensitive element (A-1) having photosensitive resin composition layer containing phosphor] The materials shown in Table 2 were mixed, and the mixture was mixed for 15 minutes using a raikai machine. The mixture was mixed to prepare a photosensitive resin composition solution containing a phosphor.

[0155]

[Table 2]

The obtained solution was uniformly coated on a polyethylene terephthalate film having a thickness of 20 μm.
The solvent was removed by drying with a hot air convection dryer at 〜110 ° C. for 10 minutes to form (A) a photosensitive resin composition layer containing a phosphor. The thickness of the obtained layer (A) after drying is 60
μm. Next, on the (A) layer, a thickness of 25 μm
(A) A photosensitive element (A-1) having a photosensitive resin composition layer containing a phosphor was prepared.

Production Example 3 [(A) Production of photosensitive element (A-2) having photosensitive resin composition layer containing phosphor] Instead of the material shown in Table 2, the material shown in Table 3 was used. Production Example 2 except for
In the same manner as in (1), a photosensitive resin composition layer containing the phosphor (A) was formed. The thickness of the obtained (A) layer after drying is
It was 60 μm.

[0158]

[Table 3]

Next, in the same manner as in Production Example 2, (A) a photosensitive element (A-2) having a photosensitive resin composition layer containing a phosphor was prepared.

Production Example 4 [(A) Production of photosensitive element (A-3) having photosensitive resin composition layer containing phosphor] In place of the material shown in Table 2, the material shown in Table 4 was used. Production Example 2 except for
In the same manner as in (1), a photosensitive resin composition layer containing the phosphor (A) was formed. The thickness of the obtained (A) layer after drying is
It was 60 μm.

[0161]

[Table 4]

Next, in the same manner as in Production Example 2, (A) a photosensitive element (A-3) having a photosensitive resin composition layer containing a phosphor was prepared.

Production Example 5 [Preparation of Resin Composition (B-1) Containing (C) Fine Particles] A resin solution composed of the materials shown in Table 5 was mixed until uniformly dispersed. Resin composition (B
-1) was prepared.

[0164]

[Table 5]

Production Example 6 [(C) Film having resin layer containing fine particles (B
-2) Preparation of a resin solution composed of the materials shown in Table 6
It is uniformly coated on a polyethylene terephthalate film having a thickness of 0 μm, dried with a hot air convection dryer at 80 to 110 ° C. for 10 minutes to remove the solvent, and (C) forms a layer of a resin composition containing fine particles. did. The thickness of the obtained layer (C) after drying was 43 μm.

[0166]

[Table 6]

Next, on the layer (C), a thickness of 25 μm
(C) A film (B-2) having a resin layer containing fine particles was prepared by laminating the polyethylene film as a cover film.

Production Example 7 [(C) Film having resin layer containing fine particles (B)
Production of -3)] (C) in the same manner as in Production Example 6 except that the materials shown in Table 7 were used instead of the materials shown in Table 6.
A layer of a resin composition containing fine particles was formed. The thickness of the obtained layer (C) after drying was 50 μm.

[0169]

[Table 7]

Next, a film (B-3) having a resin layer containing fine particles (C) was produced in the same manner as in Production Example 6.

Production Example 8 [(C) Film having resin layer containing fine particles (B)
Production of -4)] (C) in the same manner as in Production Example 6 except that the materials shown in Table 8 were used instead of the materials shown in Table 6.
A layer of a resin composition containing fine particles was formed. The thickness of the obtained layer (C) after drying was 50 μm.

[0172]

[Table 8]

Next, a film (B-4) having a resin layer containing fine particles (C) was produced in the same manner as in Production Example 6.

Production Example 9 [(C) Film having resin layer containing fine particles (B)
Production of -5)] (C) in the same manner as in Production Example 6 except that the materials shown in Table 9 were used instead of the materials shown in Table 6.
A layer of a resin composition containing fine particles was formed. The thickness of the obtained layer (C) after drying was 50 μm.

[0175]

[Table 9]

Next, a film (B-5) having a resin layer containing fine particles (C) was produced in the same manner as in Production Example 6.

Production Example 10 [Film having (A) photosensitive resin composition layer containing phosphor and (C) resin layer containing fine particles (E-
Production of 1)] The cover film of the film (B-5) having a layer of the resin composition containing fine particles (C) obtained in Production Example 9 is peeled off, and the resin composition containing fine particles (C) is removed. On the layer, a photosensitive resin composition solution containing a phosphor composed of the material shown in Table 3 was uniformly applied, and dried with a hot air convection dryer at 80 to 110 ° C. for 10 minutes to remove the solvent.
(A) A photosensitive resin composition layer containing a phosphor was formed. The thickness of the obtained layer (A) after drying was 60 μm.

Next, a 25 μm-thick polyethylene film is laminated as a cover film on the (A) phosphor-containing photosensitive resin composition layer, and (A) the phosphor-containing photosensitive resin composition A film (E-1) having a layer and a resin layer containing (C) fine particles was prepared.

Production Example 11 [Film having (A) photosensitive resin composition layer containing phosphor and (C) resin layer containing fine particles (E-
2) Production] A resin solution composed of the material shown in Table 10 was mixed with 2
It is uniformly coated on a polyethylene terephthalate film having a thickness of 0 μm, dried with a hot air convection dryer at 80 to 110 ° C. for 10 minutes to remove the solvent, and (C) forms a layer of a resin composition containing fine particles. did. The thickness of the obtained layer (C) after drying was 50 μm.

[0180]

[Table 10]

Next, a polyethylene film having a thickness of 25 μm was laminated as an intermediate layer on the resin layer containing the fine particles (C).
The photosensitive resin composition solution containing the phosphor composed of the material shown in (1) is uniformly applied and dried with a hot air convection dryer at 80 to 110 ° C. for 10 minutes to remove the solvent. A photosensitive resin composition layer was formed. Obtained (A)
The dried thickness of the layer was 50 μm.

Next, a 20 μm-thick polyethylene film is laminated as a cover film on the (A) phosphor-containing photosensitive resin composition layer, and (A) the phosphor-containing photosensitive resin composition A film (E-2) having a layer and a resin layer containing (C) fine particles was prepared.

Comparative Production Example 1 [(C ') Resin composition containing no fine particles (B'-1)
Preparation of] A resin solution composed of the materials shown in Table 11 was mixed until it became uniform, to prepare a resin composition (B'-1) containing no (C ') fine particles.

[0184]

[Table 11]

Comparative Production Example 2 [(C ') Production of Film (B'-2) Having Resin Layer Containing No Fine Particles] Instead of the materials shown in Table 6, Table 1
Except for using the material shown in 2, the same as in Production Example 6,
(C ′) A layer of a resin composition containing no fine particles was formed. The thickness of the obtained layer (C ′) after drying was 43 μm.

[0186]

[Table 12]

Next, in the same manner as in Production Example 6, (C ′)
Film having a resin layer containing no fine particles (B'-
2) was produced.

Comparative Production Example 3 [(C ') Production of Film (B'-3) Having Resin Layer Containing No Fine Particles] Instead of the materials shown in Table 7, Table 1
In the same manner as in Production Example 7 except that the materials shown in No. 3 were used,
(C ′) A layer of a resin composition containing no fine particles was formed. The thickness of the obtained layer (C ′) after drying was 50 μm.

[0189]

[Table 13]

Next, in the same manner as in Production Example 6, (C ′)
Film having a resin layer containing no fine particles (B'-
3) was produced.

Comparative Production Example 4 [(C ') Production of Film (B'-4) Having Resin Layer Containing No Fine Particles] Instead of the materials shown in Table 8, Table 1
In the same manner as in Production Example 8 except that the materials shown in Example 4 were used,
(C ′) A layer of a resin composition containing no fine particles was formed. The thickness of the obtained layer (C ′) after drying was 50 μm.

[0192]

[Table 14]

Next, in the same manner as in Production Example 6, (C ′)
Film having a resin layer containing no fine particles (B'-
4) was produced.

Comparative Production Example 5 [(C ') Production of Film (B'-5) Having Resin Layer Containing No Fine Particles] Instead of the materials shown in Table 9, Table 1
Except for using the material shown in 5, the same as in Production Example 9
(C ′) A layer of a resin composition containing no fine particles was formed. The thickness of the obtained layer (C ′) after drying was 50 μm.

[0195]

[Table 15]

Next, in the same manner as in Production Example 6, (C ′)
Film having a resin layer containing no fine particles (B'-
5) was produced.

Comparative Production Example 6 [Production of film (E'-1) having (A) photosensitive resin composition layer containing phosphor and (C ') resin layer not containing fine particles] Obtained in Production Example 9 Instead of the obtained film (B-5) having a resin layer containing fine particles (C-5), a film (B'-5) having a resin layer containing no (C ') fine particles obtained in Comparative Production Example 5 A film having (A) a photosensitive resin composition layer containing a phosphor (thickness: 60 μm) and a resin layer containing no (C ′) fine particles (thickness: 50 μm) in the same manner as in Production Example 10 except that E'-1) was prepared.

Comparative Production Example 7 [Preparation of (A) Film (E'-2) having photosensitive resin composition layer containing phosphor and (C ') resin layer not containing fine particles] Materials shown in Table 10 Table 16
In the same manner as in Production Example 11 except that the materials shown in
(A) Photosensitive resin composition layer containing phosphor (thickness 50
μm), an intermediate layer (thickness 25 μm), and a film (E′-2) having a resin layer (thickness 50 μm) containing no (C ′) fine particles.

[0199]

[Table 16]

[Preparation of Phosphor Pattern] Example 1 [(Ia) Step of Forming (A) Photosensitive Resin Composition Layer Containing Phosphor on Irregular Surface of Substrate Having Irregularities] P
On the side on which the barrier ribs of the DP substrate (striped barrier ribs, opening width between barrier ribs 150 μm, barrier rib width 70 μm, barrier rib height 150 μm) are formed,
After placing the photosensitive element (A-1) having the photosensitive resin composition layer containing the phosphor (A) obtained in Production Example 2 while peeling off the polyethylene terephthalate film, peeling off the polyethylene film and vacuum drying The pressure was reduced to 1 × 10 ² Pa at room temperature in a machine. Then, under reduced pressure, the temperature was raised to 90 ° C. at a rate of 5 ° C./min,
After maintaining at 90 ° C. for 1 minute, the pressure was returned by returning the pressure to the atmospheric pressure, whereby (A) the photosensitive resin composition layer containing the phosphor was formed on the inner surface of the concave portion.

[(Ib) Step of Forming (C) Resin Layer Containing Fine Particles on Photosensitive Resin Composition Layer Containing (A) Phosphor] (A) Photosensitive Resin Composition Containing Phosphor Resin composition containing (C) fine particles on the material layer (B-1)
Was spin-coated at 300 rpm for 1 minute.
The substrate was dried with a hot air convection dryer at 110 ° C. for 10 minutes to remove distilled water, and (A) the concave portion was sufficiently buried on the photosensitive resin composition layer containing the phosphor (C).
A resin layer containing fine particles was formed.

[(II) Step of irradiating actinic ray imagewise to (A) resin layer containing fine particles and (A) photosensitive resin composition layer containing phosphor] Next, (C) containing fine particles On the layer of the resin composition to be formed, the opening width 15 between the barrier ribs is set.
A photomask having an active light transmission width of 15 μm narrower than 0 μm is brought into close contact with the center of the opening width between the barrier ribs such that the center of the active light transmission width of the photomask is located, and HMW-201GX manufactured by Oak Manufacturing Co., Ltd. Irradiation with actinic rays was performed imagewise at 400 mJ / cm ² using a mold exposure machine.

[(III) Step of forming a pattern by removing the resin layer containing the fine particles (C) and selectively removing the photosensitive resin composition layer containing the phosphor (A) by development] After standing at room temperature for 1 hour, spray development was performed at 30 ° C. for 120 seconds using a 1% by weight aqueous sodium carbonate solution, and the layer (C) and the layer (A) were selectively removed by development to form a pattern. . After the development, the film was dried at 80 ° C. for 10 minutes, irradiated with ultraviolet rays of 3 J / cm ² by using a Toshiba UV irradiator manufactured by Toshiba Electric Materials Co., Ltd., and further heated in a dryer at 150 ° C. for 1 hour.

[(IV) Step of Removing Organic Components by Firing] Next, heat treatment (firing) is performed at 550 ° C. for 30 minutes to remove unnecessary resin components, and a phosphor pattern is formed in the space of the PDP substrate. Formed.

[Evaluation of Phosphor Pattern] The cross section of the obtained phosphor pattern was visually observed with a stereoscopic microscope and an SEM to evaluate the formation state of the phosphor pattern. The results are shown in Table 17. The evaluation criteria are as follows. ：: The phosphor layer is uniformly formed on the inner surface of the concave portion (the barrier rib wall surface and the substrate surface) of the PDP substrate. X: The phosphor layer is not uniformly formed on the inner surface of the concave portion (the barrier rib wall surface and the substrate surface) of the PDP substrate.

Example 2 [(Ia) Step of Forming (A) Photosensitive Resin Composition Layer Containing Phosphor on Irregular Surface of Substrate Having Irregularities]
On the side on which the barrier ribs of the DP substrate (striped barrier ribs, opening width between barrier ribs 150 μm, barrier rib width 70 μm, barrier rib height 150 μm) are formed,
A vacuum laminator (manufactured by Hitachi Chemical Co., Ltd., with the photosensitive element (A-1) having the photosensitive resin composition layer containing the phosphor (A) obtained in Production Example 2 being peeled off the polyethylene film. Using the product name VLM-1), the heat shoe temperature is 30 ° C., and the laminating speed is 0.5 m /
The pressure was 4,000 Pa or less and the pressure (cylinder pressure) was 5 × 10 ⁴ Pa (thickness: 3 mm, length: 10 cm × width: 10 cm). The linear pressure at this time was 2.4 × 10 ³ N / m).

[(Ib) Step of Forming (C) Resin Layer Containing Fine Particles on Photosensitive Resin Composition Layer Containing (A) Phosphor] Next, (A) Photosensitivity Containing Phosphor The polyethylene terephthalate film of the photosensitive element (A-1) containing the resin composition layer is peeled off, and the film containing the resin layer containing fine particles (C) obtained in Production Example 6 on the layer (A) ( B-2), while peeling off the polyethylene film, using a laminator (manufactured by Hitachi Chemical Co., Ltd., trade name: HLM-3000), the laminating speed is 0.5 m / min, and the pressing pressure is gauge pressure (cylinder pressure). 4 × 10 ⁵ Pa (thickness 3 mm, length 10 at normal pressure 1 atm is 0)
Since a substrate measuring 10 cm × 10 cm was used, the linear pressure at this time was 9.
(8 × 10 ³ N / m) to form a layer (A) and a layer (C) on the inner surface of the recess.

[(II) Step of irradiating actinic ray imagewise to resin layer containing (C) fine particles and photosensitive resin composition layer containing (A) phosphor] Then, (C) fine particles are contained. On the polyethylene terephthalate film of the film (B-2) having a resin layer, the opening width between the barrier ribs is 15
A photomask having an active light transmission width of 15 μm narrower than 0 μm is brought into close contact with the center of the opening width between the barrier ribs such that the center of the active light transmission width of the photomask is located, and HMW-201GX manufactured by Oak Manufacturing Co., Ltd. Irradiation with actinic rays was performed imagewise at 400 mJ / cm ² using a mold exposure machine.

[(III) Step of forming a pattern by removing the resin layer containing the fine particles (C) and selectively removing the photosensitive resin composition layer containing the phosphor (A) by development] After leaving at room temperature for 1 hour, the polyethylene terephthalate film of the film (B-2) having a resin layer containing fine particles (C) was peeled off, and sprayed at 30 ° C. for 120 seconds using a 1% by weight aqueous solution of sodium carbonate. After development, the layer (C) and the layer (A) were selectively removed by development to form a pattern. After the development, the film was dried at 80 ° C. for 10 minutes, irradiated with ultraviolet rays of 3 J / cm ² by using a Toshiba UV irradiator manufactured by Toshiba Electric Materials Co., Ltd., and further heated in a dryer at 150 ° C. for 1 hour.

[(IV) Step of Removing Organic Components by Firing] Next, heat treatment (firing) is performed at 550 ° C. for 30 minutes to remove unnecessary resin components, and a phosphor pattern is formed in the space of the PDP substrate. Formed.

[Evaluation of Phosphor Pattern] The cross section of the obtained phosphor pattern was evaluated in the same manner as in Example 1 to evaluate the state of formation of the phosphor pattern. The results are shown in Table 17.

Example 3 In Example 2, the photosensitive element (A) having the (A) phosphor-containing photosensitive resin composition layer in the step (I) was used.
-1) Photosensitive element (A-2) having photosensitive resin composition layer containing phosphor (A) obtained in Production Example 3 (A-2)
And a phosphor pattern was formed in the same manner as in Example 2 except that the step (II) was changed as shown below.
The obtained phosphor pattern was evaluated, and the results are shown in Table 17.

[(II) Step of irradiating actinic ray imagewise on (A) resin layer containing fine particles and (A) photosensitive resin composition layer containing phosphor] (C) Resin containing fine particles On the polyethylene terephthalate film of the film (B-2) having a layer, the opening width between the barrier ribs is 150 μm.
A photomask having an active light transmission width smaller than 30 μm than the photomask having the center of the active light transmission width of the photomask positioned at the center of the opening width between the barrier ribs.
Using Oak Manufacturing HMW-201GX type exposure machine,
An actinic ray of 400 mJ / cm ² was irradiated imagewise.

Example 4 In Example 3, the photosensitive element (A) having the (A) phosphor-containing photosensitive resin composition layer in the step (I) was used.
-2) A photosensitive element (A-3) having a photosensitive resin composition layer containing a phosphor obtained in Production Example 4 (A-3)
The film (B-2) having the resin layer containing fine particles (B-2) was replaced with the film (B-3) having the resin layer containing fine particles (C) obtained in Production Example 7, II
Example 3 except that the step of I) was changed as shown below
A phosphor pattern was formed in the same manner as described above, and the obtained phosphor pattern was evaluated. The results are shown in Table 17.

[(III) Step of forming a pattern by removing the resin layer containing fine particles (C) and selectively removing the photosensitive resin composition layer containing the phosphor (A) by development] After irradiating with light, leave at room temperature for 1 hour,
(C) Film having resin layer containing fine particles (B-
3) Peeling off the polyethylene terephthalate film,
Using an emulsion solution consisting of 3-methyl-3-methoxybutyl acetate and water (3-methyl-3-methoxybutyl acetate / water (weight ratio) = 25/75),
Spray development was performed at 30 ° C. for 70 seconds, and the layer (C) and the layer (A) were selectively removed by development to form a pattern.
After the development, the film was dried at 80 ° C. for 10 minutes, and irradiated with ³ J / cm ² ultraviolet rays using a Toshiba UV irradiator manufactured by Toshiba Electronics Corporation. went.

Example 5 A phosphor pattern was prepared in the same manner as in Example 1 except that the steps (Ia), (Ib) and (II) were changed as follows. Was formed, and the obtained phosphor pattern was evaluated. The results are shown in Table 17.

[(Ia) Step of Forming (A) Photosensitive Resin Composition Layer Containing Phosphor on Irregular Surface of Substrate Having Irregularities] PDP substrate (stripe-shaped barrier ribs, opening width between barrier ribs 150 μm , Barrier rib width 70μ
m, the material shown in Table 3 in Production Example 3 was mixed in the region where the barrier ribs (having a height of 150 μm) were mixed,
A phosphor-containing photosensitive resin paste (AP-2) obtained by mixing for 15 minutes using a Raikai machine was screen-printed (SSA-PC1310A manufactured by Tokai Seiki Co., Ltd.).
N, screen mesh = 100 μm, squeegee speed =
Screen printing was performed at 10 cm / sec, attack angle = 75 degrees). Next, heating was performed at 80 ° C. for 15 minutes to form (A) a photosensitive resin composition layer containing a phosphor on the inner surface of the concave portion.

[(Ib) Step of Forming (C) Resin Layer Containing Fine Particles on Photosensitive Resin Composition Layer Containing (A) Phosphor] (A) Photosensitive Resin Composition Containing Phosphor Resin composition containing (C) fine particles on the material layer (B-1)
Screen printing machine (SSA-PC13 manufactured by Tokai Seiki Co., Ltd.)
10AN, screen mesh = 100 μm, squeegee speed = 10 cm / sec, attack angle = 75 °). The substrate was dried with a hot air convection dryer at 110 ° C. for 10 minutes to remove distilled water, and (C) was placed on the surface of the concave portion where the photosensitive resin composition layer containing the phosphor was formed.
A resin layer containing fine particles was sufficiently embedded to form a (C) layer.

[(II) Step of irradiating actinic ray imagewise to resin layer containing (C) fine particles and photosensitive resin composition layer containing (A) phosphor] Next, (C) containing fine particles A photomask having an active light transmission width 30 μm narrower than the opening width 150 μm between the barrier ribs is placed on the resin layer to be formed, and the center of the opening width between the barrier ribs at a position spaced 100 μm upward from the layer (C). Is positioned so that the center of the active light transmission width of the photomask is located at
Using an HMW-590 type exposure machine manufactured by Oak Manufacturing Co., Ltd., 40
Actinic light was irradiated imagewise at 0 mJ / cm ² .

Example 6 A phosphor pattern was formed and obtained in the same manner as in Example 5, except that the step (Ib) and the step (III) were changed as described below. The phosphor pattern was evaluated, and the results are shown in Table 17.

[(Ib) Step of Forming (C) Resin Layer Containing Fine Particles on Photosensitive Resin Composition Layer Containing (A) Phosphor] (A) Photosensitive Resin Composition Containing Phosphor A film (B-4) having a resin layer containing fine particles (C) obtained in Production Example 8 on the material layer was peeled off from the polyethylene film while a laminator (Hitachi Chemical Industry Co., Ltd.) was used.
Lamination speed is 0.5 m / min and the pressure is gauge pressure (cylinder pressure, normal pressure 1 atm is 0) and 4 × 10 ⁵ Pa (thickness is 3 m).
m, a substrate measuring 10 cm in length and 10 cm in width was used. The linear pressure at this time was 9.8 × 10 ³ N / m), and the (C) layer was formed on the (A) layer.

[(III) Step of forming a pattern by removing the resin layer containing the fine particles (C) and selectively removing the photosensitive resin composition layer containing the phosphor (A) by development] (C) A film having a resin layer containing fine particles (C) by adhering an adhesive film on the polyethylene terephthalate film on the film (B-4) having a resin layer containing fine particles (B-4). -4) was peeled off. Then, after leaving at room temperature for 1 hour, 1% by weight
Using a sodium carbonate aqueous solution, spray development was performed at 30 ° C. for 50 seconds, and the layer (A) was selectively removed to form a pattern. After development, dry at 80 ° C for 10 minutes.
Ultraviolet irradiation of 3 J / cm ² was performed using a Toshiba ultraviolet irradiator manufactured by Toshiba Corporation.

Example 7 A phosphor pattern was formed in the same manner as in Example 5, except that the step (Ia) was changed as described below, and the obtained phosphor pattern was evaluated. The results are shown in Table 17.

[(Ia) Step of Forming (A) Photosensitive Resin Composition Layer Containing Phosphor on Irregular Surface of Substrate Having Irregularities] PDP substrate (stripe-shaped barrier ribs, opening width between barrier ribs 150 μm , Barrier rib width 70μ
m, the photosensitive element (A-) having the photosensitive resin composition layer containing the phosphor (A) obtained in Production Example 2 on the side where the barrier rib having a barrier rib height of 150 μm is formed.
After 1) was mounted while the polyethylene terephthalate film was peeled off, the polyethylene film was peeled off, put in a vacuum dryer, and the pressure was reduced to 1 × 10 ² Pa at room temperature. Then, at a temperature rising rate of 5 ° C./min at a reduced pressure, 90 ° C.
After the temperature was raised to 90 ° C. for 1 minute, the pressure was applied by returning the pressure to the atmospheric pressure to form (A) the photosensitive resin composition layer containing the phosphor on the surface of the concave portion.

Example 8 In Example 2, the steps (Ia), (Ib),
A phosphor pattern was formed in the same manner as in Example 2 except that the steps (II) and (III) were changed as described below, and the obtained phosphor pattern was evaluated. The results are shown in Table 17.

[(Ia) Step of Forming (A) Photosensitive Resin Composition Layer Containing Phosphor on Irregular Surface of Substrate with Irregularities] PDP substrate (stripe-shaped barrier ribs, opening width between barrier ribs 150 μm , Barrier rib width 70μ
m, the photosensitive element (A-) having the photosensitive resin composition layer containing the phosphor (A) obtained in Production Example 2 on the side where the barrier rib having a barrier rib height of 150 μm is formed.
1) While peeling off the polyethylene film, a laminator (HLM-3000, manufactured by Hitachi Chemical Co., Ltd.)
The laminator roll temperature is 70 ° C., the laminating speed is 0.5 m / min, and the pressing pressure is 2 × 10 ⁵ Pa (thickness is 3) at gauge pressure (cylinder pressure, normal pressure 1 atm is 0).
Since a substrate measuring 10 mm in length and 10 cm in width and 10 cm in width was used, the linear pressure at this time was 4.9 × 10 ³ N / m), and (A) the photosensitive resin composition layer containing the phosphor was laminated. . Thereafter, the polyethylene terephthalate film as the support film was peeled off, and the substrate was heated at 80 ° C. for 10 minutes.

[(Ib) Step of Forming (C) Resin Layer Containing Fine Particles on Photosensitive Resin Composition Layer Containing (A) Phosphor] Then, a production example is formed on (A) layer. (C) Film containing resin layer containing fine particles (B) obtained in (8)
-4), while peeling off the polyethylene film, a laminator (HLM-3000, manufactured by Hitachi Chemical Co., Ltd.)
Using a mold, the laminating speed was 0.5 m / min and the pressing pressure was 4 × 10 ⁵ Pa (thickness 3 mm, vertical 10 cm × horizontal 10 cm) at gauge pressure (cylinder pressure, normal pressure 1 atm is 0). Because the substrate was used, the linear pressure at this time was 9.8 × 10 ³ N / m), and the layers (A) and (C) were formed on the inner surface of the recess.

[(II) Step of irradiating actinic ray imagewise to resin layer containing fine particles (C) and photosensitive resin composition layer containing fluorescent material (A)] (C) Fine particles containing fine particles On the resin layer to be formed, a photomask having an active light transmission width smaller than 30 μm than the opening width between the barrier ribs by 150 μm is placed between the barrier ribs at a distance of 300 μm upward from the polyethylene terephthalate film on the layer (C). Is arranged such that the center of the actinic ray transmission width of the photomask is located at the center of the opening width of the photomask, and the actinic ray is imaged at 400 mJ / cm ² using an HMW-590 type exposure machine manufactured by Oak Manufacturing Co., Ltd. Irradiation.

[(III) Step of forming a pattern by removing the resin layer containing the fine particles (C) and selectively removing the photosensitive resin composition layer containing the phosphor (A) by development] , (C) a film having a resin layer containing fine particles (B-) by bonding an adhesive film on the polyethylene terephthalate film on a film (B-4) having a resin layer containing fine particles, 4) was peeled off. Then, after leaving at room temperature for 1 hour, 1% by weight
Using a sodium carbonate aqueous solution, spray development was performed at 30 ° C. for 50 seconds, and the layer (A) was selectively removed to form a pattern. After development, dry at 80 ° C for 10 minutes.
Ultraviolet irradiation of 3 J / cm ² was performed using a Toshiba ultraviolet irradiator manufactured by Toshiba Corporation.

Example 9 In Example 8, the photosensitive element (A-1) having the photosensitive resin composition layer containing the phosphor (A) obtained in Production Example 2 was obtained in Production Example 3. (A) A photosensitive element (A) having a photosensitive resin composition layer containing a phosphor.
A film having a resin layer containing fine particles (C) obtained in Production Example 9 is a film (B-4) having a resin layer containing fine particles (C) obtained in Production Example 8 in place of -2). A phosphor pattern was formed in the same manner as in Example 8 except that (B-5) was used, and the obtained phosphor pattern was evaluated. The results are shown in Table 17.

Example 10 In Example 8, except that the step (Ia) and the step (Ib) were changed to the following step (I) and the step (III) was changed as shown below, In the same manner as in Example 8,
A phosphor pattern was formed, and the obtained phosphor pattern was evaluated. The results are shown in Table 17.

[(I) On a substrate having irregularities, (A)
Step of Forming a Photosensitive Resin Composition Layer Containing Phosphor and a Resin Layer Containing (C) Fine Particles sequentially] A PDP substrate (stripe-shaped barrier ribs, opening width between barrier ribs 150 μm, barrier ribs 70 μm in width,
On the side on which the barrier rib (having a barrier rib height of 150 μm) was formed, the (A) photosensitive resin composition layer containing the phosphor obtained in Production Example 10 and the (C) resin composition layer containing fine particles were obtained. While peeling off the polyethylene film of the film (E-1), a laminator (trade name: HLM-3000, manufactured by Hitachi Chemical Co., Ltd.) is in contact with the layer (A).
Laminator roll temperature is 120 ° C., laminating speed is 0.5 m / min, and pressing pressure is gauge pressure (cylinder pressure, normal pressure 1 atm is 0) and 4 × 10 ⁵ Pa (thickness is 3 mm). Since a substrate having a length of 10 cm and a width of 10 cm was used, the linear pressure at this time was 9.8 × 10 ³ N / m), and (A) a photosensitive resin composition layer containing a phosphor and (C) A resin layer containing fine particles was formed.

[(III) Step of removing the resin layer containing (C) fine particles and selectively removing (A) the photosensitive resin composition layer containing the phosphor by development to form a pattern] A pressure-sensitive adhesive film is adhered on a polyethylene terephthalate film on a film (E-1) having (A) a photosensitive resin composition layer containing a phosphor and (C) a resin layer containing fine particles, and physically. (C) The resin layer portion containing the fine particles was peeled off. Then, at room temperature,
After standing for a period of time, a 1% by weight aqueous sodium carbonate solution was used for spray development at 30 ° C. for 50 seconds, and the layer (A) was selectively removed to form a pattern. After development, at 80 ° C
After drying for 0 minutes, ultraviolet irradiation of 3 J / cm ² was performed using a Toshiba ultraviolet irradiation device manufactured by Toshiba Electric Materials Co., Ltd.

Example 11 In Example 10, a film (E-1) having (A) a photosensitive resin composition layer containing a phosphor and (C) a resin layer containing fine particles obtained in Production Example 10 In Production Example 11
Film (E) having the (A) photosensitive resin composition layer containing the phosphor and the (C) resin layer containing the fine particles obtained in
A phosphor pattern was formed in the same manner as in Example 10 except that the step (III) was changed as shown below, instead of -2), and the obtained phosphor pattern was evaluated. The results are shown in Table 17.

[(III) Step of removing the resin layer containing (C) fine particles and selectively removing the (A) photosensitive resin composition layer containing the phosphor by development to form a pattern] A pressure-sensitive adhesive film is adhered on a polyethylene terephthalate film on a film (E-2) having a photosensitive resin composition layer containing (A) a phosphor and a resin layer containing (C) fine particles, and physically. (C) The resin layer containing the fine particles and the intermediate layer were separated and removed. Then
After standing at room temperature for 1 hour, spray development was carried out at 30 ° C. for 50 seconds using a 1% by weight aqueous solution of sodium carbonate.
The layer was selectively removed to form a pattern. After development, 8
It was dried at 0 ° C. for 10 minutes, and was irradiated with ³ J / cm ² of ultraviolet light using a Toshiba ultraviolet light irradiation device manufactured by Toshiba Electric Materials Co., Ltd.

Comparative Example 1 In Example 1, the resin composition (B-1) containing the fine particles obtained in Production Example 5 was replaced with the resin composition (C ') containing no fine particles obtained in Comparative Production Example 1. A phosphor pattern was formed in the same manner as in Example 1, except that the product (B'-1) was used, and the obtained phosphor pattern was evaluated. The results are shown in Table 18.

Comparative Example 2 In Example 2, the film (B-2) having the resin composition layer containing the fine particles (C) obtained in Production Example 6 was used.
A phosphor pattern was formed in the same manner as in Example 2, except that the film (B'-2) having a resin composition layer containing no (C ') fine particles obtained in Comparative Production Example 2 was used.
The obtained phosphor pattern was evaluated, and the results are shown in Table 18.

Comparative Example 3 In Example 3, the film (B-2) having the resin composition layer containing the fine particles (C) obtained in Production Example 6 was used.
A phosphor pattern was formed in the same manner as in Example 3, except that the film (B'-2) having a resin composition layer containing no (C ') fine particles obtained in Comparative Production Example 2 was used.
The obtained phosphor pattern was evaluated, and the results are shown in Table 18.

Comparative Example 4 In Example 4, the film (B-3) having a resin composition layer containing fine particles (C) obtained in Production Example 7 was used.
A phosphor pattern was formed in the same manner as in Example 4, except that the film (B'-3) having a resin composition layer containing no (C ') fine particles obtained in Comparative Production Example 3 was used.
The obtained phosphor pattern was evaluated, and the results are shown in Table 18.

Comparative Example 5 In Example 5, the resin composition (B-1) containing the fine particles (C) obtained in Production Example 5 was replaced with the resin composition (B ′) obtained in Comparative Production Example 1. Resin composition (B'-
A phosphor pattern was formed in the same manner as in Example 5, except that 1) was used, and the obtained phosphor pattern was evaluated.
The results are shown in Table 18.

Comparative Example 6 In Example 6, the film (B-4) having the resin composition layer containing the fine particles (C) obtained in Production Example 8 was used.
A phosphor pattern was formed in the same manner as in Example 6, except that the film (B'-4) having a resin composition layer containing no (C ') fine particles obtained in Comparative Production Example 4 was used.
The obtained phosphor pattern was evaluated, and the results are shown in Table 18.

Comparative Example 7 In Example 7, the resin composition (B-1) containing the fine particles (C) obtained in Production Example 5 was replaced with the resin composition (B ′) containing the fine particles (C ′) obtained in Comparative Production Example 1. Resin composition (B'-
A phosphor pattern was formed in the same manner as in Example 7, except that 1) was used, and the obtained phosphor pattern was evaluated.
The results are shown in Table 18.

Comparative Example 8 In Example 8, the film (B-4) having a resin composition layer containing fine particles (C) obtained in Production Example 8 was used.
A phosphor pattern was formed in the same manner as in Example 8, except that the film (B'-4) having a resin composition layer containing no (C ') fine particles obtained in Comparative Production Example 4 was used.
The obtained phosphor pattern was evaluated, and the results are shown in Table 18.

Comparative Example 9 In Example 9, the film (B-5) having the resin composition layer containing the fine particles (C) obtained in Production Example 9 was used.
A phosphor pattern was formed in the same manner as in Example 9 except that the film (B′-5) having a resin composition layer containing no (C ′) fine particles obtained in Comparative Production Example 5 was used.
The obtained phosphor pattern was evaluated, and the results are shown in Table 18.

Comparative Example 10 In Example 10, a film (E-1) having (A) a photosensitive resin composition layer containing a phosphor and (C) a resin layer containing fine particles obtained in Production Example 10 Was replaced with the film (E′-1) having the (A) photosensitive resin composition layer containing the phosphor and the (C ′) resin layer not containing the fine particles obtained in Comparative Production Example 6, except that A phosphor pattern was formed in the same manner as in Example 10, and the obtained phosphor pattern was evaluated. The results are shown in Table 18.

Comparative Example 11 In Example 11, a film (E-2) having (A) the photosensitive resin composition layer containing the phosphor and (C) the resin layer containing the fine particles obtained in Production Example 11 was obtained. Was replaced by the film (E′-2) having the photosensitive resin composition layer containing the phosphor (A) and the resin layer containing the fine particles (C ′) obtained in Comparative Production Example 7, except that A phosphor pattern was formed in the same manner as in Example 11, and the obtained phosphor pattern was evaluated. The results are shown in Table 18.

[0247]

[Table 17]

[0248]

[Table 18]

Tables 17 and 18 show that Examples 1 to 11 using the resin composition containing the fine particles (C) and the film containing the resin layer containing the fine particles (C) showed the fluorescence on the inner surface of the concave portion of the PDP substrate. It can be seen that the formability of the body pattern (the property of forming a phosphor pattern with a uniform film thickness only on the inner surface of the recess surrounded by the barrier rib wall surface of the PDP substrate and the bottom surface of the substrate) is good.

In comparison, Comparative Examples 1 to 11 using a resin composition containing no (C ′) fine particles and a film containing a resin layer containing no (C ′) fine particles are shown in FIG.
As shown in (A) and (B), the photosensitive resin layer containing the phosphor on the wall surface of the barrier rib is eroded. It can be seen that the pattern could not be formed, and the formability of the phosphor pattern on the inner surface of the concave portion of the PDP substrate was poor. Reference numeral 15 denotes a phosphor pattern in which the barrier rib wall surface is eroded.

[0251]

According to the method for manufacturing a phosphor pattern according to the first aspect of the present invention, there is provided a method of embedding a substrate having irregularities such as a PDP substrate in a space (if the substrate is a PDP substrate, the phosphor on the barrier rib wall surface and the space bottom surface). (Formability of a photosensitive resin composition layer containing the same) is excellent, the yield is high, and a phosphor pattern having a uniform shape with high accuracy can be formed with a sufficient margin. Claim 2
The method for producing a phosphor pattern according to the present invention has the effects of the method for producing a phosphor pattern according to the first aspect, and is excellent in workability and environmental safety.

The method of manufacturing a phosphor pattern according to claim 3 has the effect of the method of manufacturing a phosphor pattern according to claim 1 or 2, and is further excellent in workability. The method for producing a phosphor pattern according to the fourth aspect has the effect of the method for producing a phosphor pattern according to the first or second aspect, and furthermore, film erosion (erosion of the photosensitive resin layer containing the phosphor on the wall surface of the barrier rib). ) Is excellent. The method for producing a phosphor pattern according to the fifth aspect has the effects of the method for producing a phosphor pattern according to the first, second, third or fourth aspect, and is further excellent in workability and light sensitivity.

The photosensitive element for forming a phosphor pattern according to claim 6 is capable of suppressing edge fusion and providing a PDP.
Of a substrate having irregularities such as a substrate for embedding into a space (P
In the case of a substrate for DP, the formability of a photosensitive resin composition layer containing a phosphor on the barrier rib wall surface and the space bottom surface)
This makes it possible to form a phosphor pattern having a uniform shape with high precision, with high yield, and with good workability. Claim 7
The photosensitive element for forming a phosphor pattern according to the present invention has the same effect as the photosensitive element for forming a phosphor pattern according to the sixth aspect, and is excellent in workability and light sensitivity.

The phosphor pattern according to claim 8 has a uniform shape with high accuracy and excellent luminance. The back plate for a plasma display panel according to the ninth aspect is provided with a phosphor pattern having a high precision, a uniform shape, and excellent luminance.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a PDP substrate on which barrier ribs are formed.

FIG. 2 is a schematic view showing an example of a PDP substrate on which barrier ribs are formed.

FIG. 3 is a schematic diagram showing a state in which a photosensitive resin composition layer containing a phosphor (A) is formed on an uneven surface of a substrate having unevenness.

FIG. 4 is a schematic view showing an example of each step of a method for manufacturing a phosphor pattern.

FIG. 5 is a schematic diagram showing an opening width of a concave portion.

FIG. 6 is a schematic view showing a portion to be light-cured.

FIG. 7 is a schematic view showing a state after performing a step (III) in a case where a photomask 7 having an opening width larger than an opening width of a concave portion is used in the step (II) of the present invention.

FIG. 8A is a schematic view showing a state in which a multicolor pattern composed of a photosensitive resin composition layer containing a phosphor is formed.

FIG. 9 is a schematic diagram showing a state in which a multicolor phosphor pattern is formed.

FIG. 10 is a schematic view showing a state in which a layer containing no fine particles is provided to form a phosphor pattern.

FIG. 11 is a schematic view showing an example of a back plate for a plasma display panel of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Substrate 2 Barrier rib 3 Grid-shaped discharge space 4 Striped discharge space 5 Uneven surface 6 (A) Photosensitive resin composition layer having phosphor 6 ′ Photocured (A) Photosensitive resin composition layer having phosphor 6'a First color pattern 6'b Second color pattern 6'c Third color pattern 7 Photomask 8 (C) Resin layer containing fine particles 9 Active ray 10 Opening width of concave portion 11 Barrier rib width 12 Photocuring Part 13 Unnecessary part 14 Phosphor pattern 14a Phosphor pattern of first color 14b Phosphor pattern of second color 14c Phosphor pattern of third color 15 Phosphor pattern in which wall surface of barrier rib is eroded 16 ... Electrode electrode 17 ... Protective film 18 ... Dielectric layer 19 ... Display electrode 20 ... Front plate substrate

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI H01J 17/04 H01J 17/04 // C08F 20/20 C08F 20/20 (72) Inventor Seiji Tai 4-chome, Higashicho, Hitachi City, Ibaraki Prefecture 13-1 Hitachi Chemical Co., Ltd.Ibaraki Research Laboratory (72) Inventor Hiroyuki Kawakami 4-3-1 Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd.Ibaraki Research Laboratory (72) Inventor Mariko Shimamura Hitachi Ibaraki Prefecture 4-3-1, Higashi-cho, Hitachi City, Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd. (72) Inventor Yumiko Sugiura 4-3-1, Higashi-cho, Hitachi City, Ibaraki Prefecture, Japan, Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd. Naoki 394 Takasaki, Kusazaki-cho, Inashiki-gun, Ibaraki Prefecture

Claims (9)

[Claims] 1. A method according to claim 1, wherein:
Forming a photosensitive resin composition layer containing a phosphor and a resin layer containing (C) fine particles, (II) a resin layer containing (C) fine particles, and (A) a photosensitive resin containing a phosphor Imagewise irradiating the composition layer with actinic rays, (III)
(C) a step of removing the resin layer containing fine particles, selectively removing the (A) photosensitive resin composition layer containing the phosphor by development to form a pattern, and (IV) baking to remove the organic component. A method for producing a phosphor pattern, comprising the steps of removing. 2. The photosensitive resin composition according to claim 1, wherein the step (I) comprises: (I ″) having a resin layer containing (C) fine particles on a support film, and further comprising (A) a phosphor on the resin layer. A photosensitive element for forming a phosphor pattern having an object layer is laminated on a substrate having irregularities such that the layer (A) is in contact with the substrate, and the layers (A) and (C) are formed with irregularities. The method for producing a phosphor pattern according to claim 1, wherein the method is a step of forming the phosphor pattern on a substrate having the phosphor pattern. 3. The steps (I) to (III) are repeated,
The method according to claim 1 or 2, wherein after forming a multicolor pattern composed of a photosensitive resin composition layer containing a phosphor that emits red, green and blue, the step (IV) is performed to form a multicolor phosphor pattern. 3. The method for producing a phosphor pattern according to item 2. 4. The steps (I) to (IV) are repeated,
The method for producing a phosphor pattern according to claim 1 or 2, wherein a multicolor phosphor pattern that emits red, green, and blue light is formed. 5. A method according to claim 1, wherein (A) the photosensitive resin composition layer containing the phosphor is (a) a film-imparting polymer, (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group, and (c) activity. The photo-initiator which generates free radicals by irradiation with light and (d) a phosphor, and the resin layer containing (C) fine particles contains a thermoplastic resin.
5. The method for producing a phosphor pattern according to 2, 3, or 4. 6. A photosensitive element for forming a phosphor pattern, comprising, on a support film, (C) a resin layer containing fine particles and (A) a photosensitive resin composition layer containing a phosphor. 7. (A) a photosensitive resin composition layer containing a phosphor, wherein (a) a film imparting polymer, (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group, and (c) activity. A photoinitiator that generates free radicals by irradiation with light, and
7. The photosensitive element for forming a phosphor pattern according to claim 6, wherein the resin layer containing (d) a phosphor and the resin layer containing the fine particles (C) contain a thermoplastic resin. 8. A phosphor pattern manufactured by the method for manufacturing a phosphor pattern according to claim 1, 2, 3, 4, or 5. 9. A back plate for a plasma display panel comprising the phosphor pattern according to claim 8 on a substrate for a plasma display panel.