JPH1143522A - Fluophor-dispersed, ray-sensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition, showing a wide development margin when a fluorescent plane is formed, having organic component(s) easily removable in the firing process, and useful as a material for plasma display panels or the like capable of forming a fluorescent plane of high display brightness by including a fluophor, a specific polymer and the like. SOLUTION: This composition is obtained by including (A) 20 to 1500 pts.wt. of fluophor, e.g. (Y, Gd)BO3 :Eu<3+> , (B) 100 pts.wt. of a polymer having (1) carboxyl group and (2) a radicalpolymerizable unsaturated group, and (C) 10 to 400 pts.wt. of a photoradical generator, e.g., 2-2'-bis(2,4-dichlorophenyl)-4,4',5,5'- tetraphenyl-1,2'-biimidazole. One of the examples of the component B is a copolymer composed of a repeating unit having the component B(1), e.g. methacrylic acid, and a repeating unit having the component B(2), e.g. tetraethylene glycol diacrylate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a phosphor-dispersed radiation-sensitive composition, and more particularly, to a phosphor-dispersed radiation-sensitive composition suitable as a material for forming a phosphor screen in a phosphor display device such as a plasma display panel. Composition.

[0002]

2. Description of the Related Art Plasma display panels (PDPs)
Although it is a large panel, its manufacturing process is easy, it has characteristics such as wide viewing angle, self-luminous type and high display quality. Is expected to become mainstream in the near future as a display device for large wall TVs of 20 inches or more. Color PDPs generate ultraviolet light by gas discharge and emit phosphors by the ultraviolet light to enable color display. Generally, a color PDP is used for emitting red light, emitting green light, and emitting blue light on a substrate. The three color phosphor screens are provided, and the pixel units of each color are uniformly mixed as a whole. To describe the color PDP more specifically, a plurality of partitions made of an insulating material called barrier ribs are provided on the surface of a substrate made of glass or the like. A fluorescent screen is provided in the place, and an electrode for applying plasma to the fluorescent screen is arranged so that each fluorescent screen is a pixel unit. As a method for producing such a color PDP, conventionally, a screen-printing method of forming a phosphor screen by arranging a paste-like phosphor composition in each pixel unit area of a substrate surface by, for example, screen printing, A photolithography method is known in which a phosphor composition layer is formed, exposed to, for example, ultraviolet rays through a mask, and then developed to provide a phosphor screen for each pixel unit region on the substrate surface. In particular, the photolithography method is easy to form a fine pattern, and is expected to be used in the field of high-performance color PDPs. For this purpose, a phosphor-dispersed radiation-sensitive composition has been eagerly developed. Such a phosphor-dispersed radiation-sensitive composition is a paste-like composition in which a phosphor is dispersed, and examples thereof include a mixture of polyvinyl alcohol and a diazonium compound or a dichromic acid compound, and a mixture of gelatin and an organic hardened material. Composition in which a phosphor is dispersed in a vehicle such as a mixture with an agent (JP-A-5-205632)
Is known. However, when a phosphor screen for PDP is formed using this phosphor-dispersed radiation-sensitive composition, the phosphor dispersed in the composition inhibits the transmission of ultraviolet rays, and significantly lowers the sensitivity of the radiation-sensitive resin component. Therefore, it is difficult to sufficiently reach the bottom of the recess on the surface of the substrate and to sufficiently cure the resin component. As a result, the fluorescent light remaining in the recess after the subsequent development and firing steps are performed. There has been a problem that the thickness of the body layer becomes thin and sufficient display luminance cannot be obtained. Further, the width of the optimum development time (development margin) at the time of forming a pixel pattern is narrow, and it has been difficult to put it on a PDP manufacturing process practically. As another example of the phosphor-dispersed radiation-sensitive composition, a composition in which a phosphor is dispersed in a vehicle comprising an organic polymer conjugate, a photopolymerizable monomer, a photopolymerization initiator, and an organic solvent ( Japanese Patent Publication No. 8-27540 is known. However, when a phosphor screen for PDP is formed by using the phosphor-dispersed radiation-sensitive composition, after exposure and development to form a pixel pattern, a temperature of about 400 to 600 ° C. is used to remove organic components. When firing, if the composition contains a photopolymerizable monomer, the unreacted photopolymerizable monomer remaining in the phosphor layer undergoes a thermosetting reaction in the firing step, and the organic material at a predetermined temperature. It has been difficult to completely remove the components, which has ultimately caused a reduction in display luminance when the PDP emits light.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems in the prior art, and has as its object a wide developing margin at the time of forming a phosphor screen, and a method of easily removing organic components in a firing step. It is another object of the present invention to provide a phosphor-dispersed radiation-sensitive composition capable of forming a phosphor screen having a high display luminance.

[0004]

According to the present invention, there are provided the following objects: (a) a phosphor, (b) a polymer containing a carboxyl group and a radically polymerizable unsaturated group, and (c) a photoradical generator. And a phosphor-dispersed radiation-sensitive composition characterized by containing:

Hereinafter, the present invention will be described in detail. (A) Phosphor The phosphor in the present invention is not particularly limited, and an appropriate one can be selected and used.
Among such phosphors, representative examples of phosphors for red light emission include Y ₂ O ₃ : Eu ³⁺ , Y ₂ SiO ₅ : Eu ³⁺ , Y ₃ Al ₅ O ₁₂ : Eu ³⁺ ,
YVO ₄ : Eu ³⁺ , (Y, Gd) BO ₃ : Eu ³⁺ , Zn ₃ (PO ₄ ) ₂ : Mn and the like. These phosphors can be used alone or in combination of two or more. Also, typical examples of the phosphor for emitting green light include Zn ₂ SiO ₄ : Mn, BaAl ₁₂ O ₁₉ : Mn,
BaMgAl ₁₄ O ₂₃ : Mn, LaPO ₄ : (Ce, Tb), Y ₃ (Al, Ga) ₅ O ₁₂ : Tb and the like can be mentioned. These phosphors can be used alone or in combination of two or more. Further, as typical examples of the phosphor for emitting blue light, Y ₂ SiO ₅ : Ce, BaMgAl
₁₀ O ₁₇ : Eu ²⁺ , BaMgAl ₁₄ O ₂₃ : Eu ²⁺ , (Ca, Sr, Ba) ₁₀ (PO ₄ ) ₆
Cl ₂ : Eu ²⁺ , (Zn, Cd) S: Ag and the like can be mentioned. These phosphors can be used alone or in combination of two or more. The amount of the phosphor used is usually 10 to 2,000 parts by weight, preferably 20 to 1500 parts by weight, based on 100 parts by weight of the polymer having a carboxyl group and a radical polymerizable unsaturated group. In this case, if the amount of the phosphor used is less than 10 parts by weight, the phosphor density on the phosphor screen tends to be low, and it is difficult to obtain sufficient display luminance. Dirt and film residue are likely to occur on the exposed portion.

(B) Polymer In the present invention, the polymer having a (b) carboxyl group and a radical polymerizable unsaturated group (hereinafter referred to as “(b) polymer”) is the terminal and / or side of a molecular chain. It is a component having one or more carboxyl groups and one or more radically polymerizable unsaturated groups in the chain and acting as a binder in the phosphor-dispersed radiation-sensitive composition of the present invention. Various (b) polymers can be used, and an alkali-soluble resin is particularly preferable. The term “alkali-soluble” as used herein means a property that is dissolved by an alkali developer described later and has a solubility to the extent that the intended development processing is performed. Preferred examples of the alkali-soluble resin include (meth) acrylic resins, hydroxystyrene resins, and novolak resins. Among such alkali-soluble resins, specific examples of particularly preferred resins include copolymers comprising a repeating unit (A) having a carboxyl group and a repeating unit (B) having a radically polymerizable unsaturated group ( Less than,
It is called "copolymer (b-1)". Or a copolymer comprising the repeating unit (A), the repeating unit (B), and the following repeating unit (C) (hereinafter, referred to as “copolymer (b-2)”). . Both of these copolymers have a carboxyl group and a radically polymerizable unsaturated group on the side chain of the molecular chain. Further, these copolymers may be random copolymers or block copolymers. In the copolymer (b-1) and the copolymer (b-2), the repeating unit (A) is a unit for imparting alkali solubility to each copolymer. Examples of the repeating unit (A) include (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid,
Examples include units derived from unsaturated carboxylic acids such as citraconic acid, mesaconic acid, and cinnamic acid. The repeating unit (A) comprises a copolymer (b-1) and a copolymer (b-1)
One or more species can be present in 2).

The repeating unit (B) includes, for example, (B-1) monomers having an allyl group such as allyl (meth) acrylate and another radically polymerizable unsaturated group;
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol Two or more (meth) such as propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate Reacting a repeating unit formed by polymerization of monomers having an acryloyloxy group, (B-2) a repeating unit having a carboxyl group with a carboxyl group; Compound having a functional group and a radical polymerizable unsaturated group having a (hereinafter, "functional unsaturated compound" hereinafter.) May be mentioned a repeating unit formed by reacting the like. Examples of the repeating unit having a carboxyl group for forming the repeating unit (B-2) include those similar to the repeating unit (A).

In the functional unsaturated compound, examples of the functional group having reactivity with a carboxyl group include an epoxy group, a carboxylic acid chloride group, a hydroxyl group and an amino group. Among such functional unsaturated compounds, compounds having an epoxy group and a radical polymerizable unsaturated group include, for example, 1,2-epoxycyclohexylmethyl (meth) acrylate and 1,2-epoxycyclopentylmethyl (meth) Acrylate,
Glycidyl (meth) acrylate, glycidyl ethyl acrylate, allyl glycidyl ether and the like can be mentioned. Examples of the compound having a carboxylic acid chloride group and a radical polymerizable unsaturated group include (meth) acrylic acid chloride, crotonic acid chloride, and cinnamic acid chloride. Examples of the compound having a hydroxyl group and a radical polymerizable unsaturated group include, for example, allyl alcohol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate. , N-
Methylol (meth) acrylamide, 2-hydroxyethyl vinyl ether and the like can be mentioned. Examples of the compound having an amino group and a radical polymerizable unsaturated group include, for example, 2-aminoethyl (meth) acrylate,
Examples thereof include 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, and 2-aminoethyl vinyl ether. The repeating unit (B) is
One or more kinds can be present in the copolymer (b-1) and the copolymer (b-2).

Further, the repeating unit (C) is a unit for appropriately adjusting the alkali solubility of the polymer (ii).
As such a repeating unit (C), for example, methyl (meth) acrylate, ethyl (meth) acrylate,
N-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec (meth) acrylate
-Butyl, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, di (meth) acrylate (Meth) acrylates such as cyclopentanyl; 2-hydroxyethyl (meth) acrylate, 2- (meth) acrylate
Unsaturated monomers having a hydroxyl group such as hydroxypropyl and 3-hydroxypropyl (meth) acrylate; o-
Unsaturated monomers having a phenolic hydroxyl group such as hydroxystyrene, m-hydroxystyrene and p-hydroxystyrene; aromatic vinyl monomers such as styrene and α-methylstyrene; conjugated dienes such as 1,3-butadiene and isoprene And units derived from the like. The repeating unit (C) contains 1 unit in the copolymer (b-2).
More than one species can be present.

The copolymer (b-1) and the copolymer (b-1)
In 2), the content of the repeating unit (A) is usually 1 to 40% by weight, preferably 2 to 40% by weight, based on all repeating units.
30% by weight. In this case, when the content of the repeating unit (A) is less than 1% by weight, the solubility of each copolymer in an alkali developing solution is reduced, and background stains tend to be easily formed on unexposed portions. On the other hand, if it exceeds 40% by weight, the solubility of each copolymer in an alkali developing solution becomes excessive, and the fluorescent screen tends to fall off the substrate. In the copolymer (b-2), the content of the repeating unit (B) is usually from 1 to 50% by weight, preferably from 2 to 40% by weight, based on all the repeating units. The content of C) is usually from 10 to 80% by weight, preferably from 20 to 70% by weight, based on all repeating units. In the present invention, the weight average molecular weight (hereinafter, referred to as “Mw”) in terms of polystyrene by gel permeation chromatography (GPC, carrier: tetrahydrofuran) of the polymer (b) is usually 1,000 to 200,000, preferably, 2,000 to 100,000. in this case,
(B) When the Mw of the polymer is less than 1,000, the width of the development time for providing optimum development is narrowed, and the development margin tends to be small.
Scum is likely to occur around the exposed portion after development, and the sharpness of the pattern edge tends to be insufficient. In addition, background stain and film residue tend to occur in the non-exposed portion.

(C) Photo-radical generator As the photo-radical generator in the present invention, for example, benzyl, benzoin, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,
2-hydroxy-1-methyl-1-phenylpropanone-1,1- (4-isopropylphenyl) -2-hydroxy-2-methylpropanone-1,4- (2-hydroxyethoxy) phenyl- (2- (Hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propanone-1, benzophenone,
4,4′-bis (dimethylamino) benzophenone,
4,4′-bis (diethylamino) benzophenone,
3,3-dimethyl-4-methoxybenzophenone, 9-
Phenylacridine, 1,7-bis (9-acridinyl) heptane, 4-azidobenzaldehyde, 4-azidoacetophenone, 4-azidobenzalacetophenone, azidopyrene, 4-diadodiphenylamine, 4-
Diazo-4'-methoxydiphenylamine, 4-diad-3-methoxydiphenylamine, 4-azidobenzalacetone, 4-diad-3'-methoxydiphenylamine, diazidochalcone, 2,6-bis (4'-azidobenzal) cyclohexanone 2,6-bis (4'-azidobenzal) -4-methylcyclohexanone, 1,3-
Bis (4'-azidobenzal) -2-propanone, 1,
3-bis (4'-azidocinnamylidene) propanone-
2,4,4'-diazidostilbene, 2,4-diethylthioxanthone, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, benzointhio-i-butyl ether, N-
Phenylthioacridine, triphenylpyrylium perchlorate, 1,3-bis (trichloromethyl) -5
(2′-chlorophenyl) -s-triazine, 1,3-
Bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2-[(2'-furyl) vinylene] -4,6-bis (trichloromethyl) -s-triazine, 2-[( 5'-methyl-2'-furyl) vinylene] -4,6-bis (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4 '
-Chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-methoxyphenyl) -s-triazine, 2,2'-bis (2-chlorophenyl) -4,4'5, 5'-tetraphenyl-1,
2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4'5,5'-tetraphenyl-
1,2′-biimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3
H) -Quinazoline and the like. These photo-radical generators can be used alone or in combination of two or more. The amount of photo radical generator used is
(B) Usually 5 to 500 parts by weight per 100 parts by weight of the polymer.
Parts by weight, preferably 10 to 400 parts by weight. In this case, if the amount of the photo-radical generator used is less than 5 parts by weight, the crosslinking reaction cannot be sufficiently advanced by exposure, and the pixel pattern may be undercut. Occasionally, the pixels may fall off the substrate, and background contamination or film residue tends to easily occur in the non-exposed portions.

Additives The phosphor-dispersed radiation-sensitive composition of the present invention comprises the above-mentioned (A) to
(C) In addition to the components, as required, various additives such as a thermosetting resin, a curing catalyst for the thermosetting resin, an adhesion promoter, a surfactant, an antioxidant, an ultraviolet absorber, and an anti-agglomeration agent. Can be contained. Examples of the thermosetting resin include an epoxy resin, a melamine resin, a urea resin, an aniline resin, a phenol resin, an unsaturated polyester resin, and an acrylate resin. Examples of the curing catalyst for thermosetting resins include, for epoxy resins, polyamines, acid anhydrides, antimony fluoride compounds, etc., and melamine resins, urea resins, or aniline resins. For ammonium salts, alcohol amines, metal salts, organic acid salts and the like, and for unsaturated polyester resins, peroxides such as benzoyl peroxide and methyl ethyl ketone peroxide. And acrylate compounds such as azo compounds such as azoisobutyronitrile and azoisovaleronitrile; benzyls such as p, p′-dimethoxybenzyl and p, p′-dichlorobenzyl; Acetophenones such as diethoxyacetophenone and 2,2-dimethyl-2-hydroxyacetophenone It can be mentioned. Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (2-methoxyethoxy)
Silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)
-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Examples thereof include silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. Examples of the surfactant include a nonionic surfactant, a cationic surfactant,
Examples include anionic surfactants. Examples of the antioxidant include 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-
Butylphenol and the like can be mentioned. As the ultraviolet absorber, for example, 2- (3-t-butyl-5-
Methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like. Examples of the agglomeration inhibitor include sodium polyacrylate, polyethylene glycol and the like. In addition, fillers, thickeners, curing accelerators, inorganic pigments, organic pigments, dyes, and the like can be added. Each of the above additives can be used alone or in combination of two or more.

Solvent The phosphor-dispersed radiation-sensitive composition of the present invention,
Alternatively, (a) it is used as a liquid composition in which components other than the phosphor are dissolved in an appropriate solvent. Examples of the solvent include ethers, esters, ether esters,
Ketones, ketone esters, amides, amide esters, lactams, lactones, sulfoxides, sulfones, (halogenated) hydrocarbons and the like can be mentioned. More specifically, tetrahydrofuran, anisole, Dioxane, ethylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, acetates, hydroxyacetates, alkoxyacetates,
Propionates, hydroxypropionates, alkoxypropionates, lactates, ethylene glycol monoalkyl ether acetates, diethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether acetates, cyclic or acyclic Ketones, acetoacetates, pyruvates, N, N-dialkylformamides, N, N-dialkylacetamides, N-alkylpyrrolidones, γ-lactones, dialkylsulfoxides, dialkylsulfones, terpineols And a mixture of ethanol and water. These solvents can be used alone or in combination of two or more. The amount of the solvent to be used is generally 5-1000 parts by weight, preferably 10-500 parts by weight, per 100 parts by weight of the total solids of the phosphor-dispersed radiation-sensitive composition of the present invention.

The phosphor-dispersed radiation-sensitive composition of the present invention comprises:
Mixing the components (a) to (c) with the additives and the solvent used as necessary, for example, using a mixer such as a ball mill, a pebble mill, a shaker, a homogenizer, a three-roll mill, and a sand mill. Can be prepared. The phosphor-dispersed radiation-sensitive composition of the present invention,
It can be very suitably used for forming a phosphor screen in a phosphor display device such as a plasma display panel. The phosphor display device is provided with, for example, a partition and a display electrode for partitioning a discharge space on a substrate such as a glass substrate, and in a recess between adjacent partitions, the phosphor-dispersed radiation-sensitive resin composition of the present invention is used. After the phosphor layer is filled by, for example, screen printing, the phosphor layer is exposed through a mask, developed, and then baked to form a phosphor screen. Radiation used for forming the phosphor screen is preferably, for example, visible light, ultraviolet light, far ultraviolet light, or the like. Irradiation conditions such as the amount of exposure are appropriately selected according to the composition of the composition. As for the conditions of the baking treatment, the heating temperature is usually 300 to 800 ° C., preferably 400 to 600 ° C., and the heating time is usually 1 to 300 ° C.
３360 minutes, preferably 10-240 minutes. Examples of the developer used when forming the phosphor screen include, for example, aqueous solutions of alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, and tetramethylammonium hydroxide, and water.
An aqueous solution of an alkaline compound is preferred. The concentration of the aqueous solution of the alkaline compound is usually 0.005 to 5% by weight, preferably 0.01 to 3% by weight. In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to a developer composed of an aqueous solution of an alkaline compound. In the case where a developer composed of an alkaline aqueous solution is used, it is generally washed after development. The phosphor-dispersed radiation-sensitive composition of the present invention has a wide development margin when forming a phosphor screen of a phosphor display device, and is industrially advantageous. Moreover, the phosphor layer formed from the phosphor-dispersed radiation-sensitive composition of the present invention has a thickness of 3
Even if the thickness is about 0 μm, the entire surface can be uniformly cured by exposure to a deep portion of the film, and a phosphor screen having a large thickness and a high display luminance can be formed. Furthermore, the phosphor-dispersed radiation-sensitive composition of the present invention can substantially completely remove the organic components in the phosphor-dispersed radiation-sensitive composition in the firing step, and in this respect, it can form a phosphor screen having a high display luminance. Can be.

[0015]

Embodiments of the present invention will be described below more specifically with reference to examples. However, the present invention is not limited to these embodiments. The following “%” and “parts” are based on weight. Synthesis Example 1 A mixture of 200 parts of N-methyl-2-pyrrolidone, 20 parts of methacrylic acid, 70 parts of n-butyl methacrylate, and 1 part of azoisobutyronitrile was charged into an autoclave equipped with a stirrer, and stirred at room temperature until uniform. The temperature was raised to 80 ° C., and polymerization was carried out at the same temperature for 3 hours. Then, 10 parts of tetraethylene glycol diacrylate was added, and the mixture was further polymerized at 80 ° C. for 2 hours. Thereafter, the mixture was cooled to room temperature to obtain a polymer solution (polymerization yield: 98%). During this polymerization, the air shutoff and stirring with nitrogen were continued. The obtained polymer had an acid value of 76 KOH mg / g,
The value obtained by dividing the Mw of the polymer by the number of radically polymerizable unsaturated groups in 1 mol of the polymer (hereinafter, also referred to as “double bond equivalent”) is 1468, and GPC manufactured by Tosoh (trade name: HLC-8)
02A) was 30,000.
This polymer is referred to as “polymer (A-1)”.

Synthesis Example 2 N-Methyl-2-pyrrolidone 200 parts Methacrylic acid 20 parts N-butyl methacrylate 80 parts Azoisobutyronitrile 1 part A mixture of stirrer was charged into an autoclave equipped with a stirrer until it became homogeneous at room temperature. After stirring, the temperature was raised to 80 ° C., and polymerization was performed at the same temperature for 3 hours. Next, the temperature was raised to 100 ° C., and polymerization was carried out at the same temperature for another 2 hours. Thereafter, the mixture was cooled to room temperature to obtain a polymer solution (polymerization yield: 97%). During this polymerization, air shutoff and stirring were continued with nitrogen. The obtained polymer had an acid value of 86 KOHmg / g and a Mw of 50,000 measured by GPC (trade name: HLC-802A) manufactured by Tosoh Corporation.
It was 0. This polymer is referred to as “polymer (a-1)”.

[0017]

【Example】

Example 1 A phosphor-dispersed radiation-sensitive composition shown below was applied on a 2.0-mm-thick glass substrate having predetermined electrodes and ribs by screen printing, and then applied in a clean oven at 100 ° C. for 10 minutes. After drying, a phosphor layer was formed. Phosphor-dispersed radiation-sensitive composition • Phosphor (Y, Gd) BO ₃ : Eu ³⁺ (red) 40 parts Polymer A-1 (Synthesis Example 1) 7.5 parts Photoradical generator 2,2 '-Bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole (this is referred to as "Component (B-1)") 1 part 4 , 4'-Diethylaminobenzophenone 1 part 2-mercaptobenzothiazole 0.5 part Solvent N-methyl-2-pyrrolidone 50 parts The obtained phosphor layer has a uniform thickness of about 30 μm on the side and bottom of the rib. Had been formed. The phosphor layer is irradiated with ultraviolet light (i.
Line, wavelength 365 nm) at an exposure of 400 mJ / cm ² . Next, after developing with a 0.05% aqueous solution of potassium hydroxide (pH 11.7) for 2 minutes, shower washing with ultrapure water is performed for 1 minute to remove the phosphor layer in the non-exposed area. Dried in. The development margin at this time was 50 seconds. Then, after heating in a 180 ° C. clean oven for 30 minutes, a baking treatment was further performed in a baking furnace at 500 ° C. for 30 minutes to form a phosphor screen for light emission, thereby producing a plasma display panel. In the obtained plasma display panel, the phosphor screen is uniformly formed on the glass substrate and on the side wall of the partition with a thickness of about 25 μm, has a sufficient thickness, and almost completely removes organic components in the firing step. And exhibited high display brightness during operation. Table 1 shows the above results.

Example 2 A phosphor-dispersed radiation-sensitive composition was prepared and a plasma display panel was prepared in the same manner as in Example 1 except that the phosphor was changed to those shown in Table 1. The obtained phosphor layer had a uniform thickness of about 30 μm on the side and bottom of the rib. The development margin when exposing and developing the phosphor layer was 55 seconds. Further, the obtained plasma display panel has a phosphor screen uniformly on the glass substrate and on the side wall of the partition wall at about 26 μm.
, And had a sufficient thickness. Organic components could be almost completely removed in the firing step, and high display luminance was exhibited during operation. Table 1 shows the above evaluation results.

Example 3 A phosphor-dispersed radiation-sensitive composition was prepared and a plasma display panel was prepared in the same manner as in Example 1 except that the following phosphor-dispersed radiation-sensitive composition was used. Phosphor-dispersed radiation-sensitive composition / Phosphor BaMgAl ₁₄ O ₂₃ : Eu ²⁺ (blue) 35 parts Polymer ACA-250M manufactured by Daicel Chemical Industries, Ltd. (trade name; acid value 29 KOHmg / g, double bond) Methacrylic acid component-containing polymer having an equivalent weight of 381 (this is referred to as “polymer (A-2)”) 10 parts Photoradical generator component (B-1) 2 parts 4,4′-diethylaminobenzophenone 2 parts 2 -1 part of mercaptobenzothiazole-50 parts of solvent N-methyl-2-pyrrolidone The obtained phosphor layer had a uniform thickness of about 25 µm on the side and bottom of the rib. The development margin when exposing and developing this phosphor layer is 65
Seconds. In the obtained plasma display panel, the fluorescent screen is uniformly formed on the glass substrate and on the side wall of the partition with a thickness of about 23 μm, and has a sufficient thickness.
In addition, organic components were almost completely removed in the firing step, and high display luminance was exhibited during operation. Table 1 shows the above evaluation results.

Example 4 (b) Preparation of a phosphor-dispersed radiation-sensitive composition and preparation of a plasma display panel were performed in the same manner as in Example 1 except that the polymer and the photoradical generator were changed to those shown in Table 1. Fabrication was performed. The obtained phosphor layer had a uniform thickness of about 25 μm on the side and bottom of the rib.
The development margin when exposing and developing this phosphor layer was 50 seconds. Further, in the obtained plasma display panel, the phosphor screen is uniformly formed on the glass substrate and on the side wall of the partition with a film thickness of about 23 μm,
It had a sufficient thickness and was able to almost completely remove organic components in the firing step, and exhibited high display luminance during operation. Table 1 shows the above evaluation results.

Comparative Example 1 A phosphor-dispersed radiation-sensitive composition was prepared and a plasma display panel was prepared in the same manner as in Example 1, except that the following phosphor-dispersed radiation-sensitive composition was used. Phosphor-dispersed radiation-sensitive composition • Phosphor (Y, Gd) BO ₃ : Eu ³⁺ (red) 40 parts Polymer a-1 (Synthesis Example 2) 3.5 parts Photopolymerizable monomer Penta Erythritol triacrylate 3.5 parts Photoradical initiator component (B-1) 1 part 4,4'-diethylaminobenzophenone 1 part 2-mercaptobenzothiazole 0.5 part Solvent N-methyl-2-pyrrolidone 50 parts The phosphor layer thus formed was uniformly formed on the side and bottom of the rib with a film thickness of about 25 μm. However, when the phosphor layer was exposed and developed, the development margin was 4 μm.
5 seconds. Further, in the obtained plasma display panel, the film phosphor screen was uniformly formed on the glass substrate and the side wall of the partition with a film thickness of about 20 μm. The display brightness was low. Table 2 shows the above evaluation results.

Comparative Example 2 Phosphor, photopolymerizable monomer and photoradical generator are shown in Table 2.
Preparation of a phosphor-dispersed radiation-sensitive composition and preparation of a plasma display panel were carried out in the same manner as in Comparative Example 1 except that the composition was changed to that shown in (1). Although the obtained phosphor layer was uniformly formed on the side and bottom of the rib with a thickness of about 25 μm, the development margin when the phosphor layer was exposed and developed was 20 seconds. Was. Also, in the obtained plasma display panel, the phosphor screen was uniformly formed on the glass substrate and the side wall of the partition with a thickness of about 20 μm, but the organic component could not be sufficiently removed in the firing step,
Display brightness during operation was low. Table 2 shows the above evaluation results.
Shown in

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[Table 1]

[0024]

[Table 2]

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The phosphor-dispersed radiation-sensitive composition of the present invention has a wider development margin when forming a phosphor screen and an organic component in the firing step, as compared with the conventional phosphor-dispersed radiation-sensitive composition. Can be easily removed, and
A sufficient film thickness can be obtained even after the development and firing steps, and a phosphor screen with high display luminance can be formed. Therefore, the phosphor-dispersed radiation-sensitive composition of the present invention greatly contributes to the increase in the size and definition of a phosphor display device such as a plasma display panel, which is expected to progress more and more in the future.

Claims (1)

[Claims] (1) a phosphor, (b) a polymer having a carboxyl group and a radically polymerizable unsaturated group, and (c)
A phosphor-dispersed radiation-sensitive composition comprising a photoradical generator.