JPH11185616A - Manufacture of phosphor pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide phosphor patterns having no chrominance change even if the phosphors buried in cells immediately before are mixed in the recovered phosphors with a good yield by forming the phosphor patterns in red for a first color, in blue for a second color, and in green for, a third color in sequence. SOLUTION: A phosphor is not limited in particular, and the phosphor mainly made of a normal metal oxide is used, e.g. Y2 O2 S is used for the red luminous phosphor, ZnS: Cu for the blue luminous phosphor, and ZnS: Ag for the green luminous phosphor. When the other luminous phosphor is mixed into each luminous phosphor, the upper limit of the phosphor mixed quantity causing no chrominance change is the red or blue phosphor at 10 wt.% or below against the green phosphor, or the total of the red and green phosphors at 5 wt.% or below. When the red phosphor is kept at 10 wt.% or below against the blue phosphor, no chrominance change occurs.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a phosphor pattern, a phosphor pattern, a CRT display, a field emission display, a fluorescent display, a radio emission display, and a back plate for a plasma display panel.

[0002]

2. Description of the Related Art The present invention will be described below by taking a plasma display panel as an example.

Conventionally, as one of the flat panel displays, a plasma display panel (hereinafter, referred to as a PDP) which is capable of performing multicolor display by providing a phosphor which emits light by plasma discharge is known.

In a PDP, a flat front plate and a rear plate made of glass are arranged 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 back plate and the barrier ribs.

[0005] In such a space, a phosphor for display is applied, and the phosphor is caused to emit light by ultraviolet rays generated from the sealed gas by discharge, so that the light can be visually recognized by an observer.

Conventionally, as a method of providing this phosphor,
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-dispersed slurry liquid is in a liquid state, poor dispersion due to precipitation of the phosphor or the like is apt to occur, and when a liquid photosensitive resist is used as the slurry liquid, the dark reaction is accelerated. It has disadvantages such as poor storage 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 (JP-A-6-267421).
And JP-A-6-273925).

[0009] The method using a liquid resist means that the components constituting the photosensitive resin composition containing the phosphor are dissolved or mixed in a solvent that can be dissolved or dispersed to form a uniformly dispersed solution. It is applied directly to the PDP substrate and dried to form a phosphor pattern.

[0010] The method using a photosensitive element means that a photosensitive resin layer containing a phosphor of a photosensitive element comprising a photosensitive resin layer containing a phosphor and a support film is heated and pressed (laminated). Embedding in the space of the PDP substrate, then, using a negative film, imagewise exposing with actinic light such as ultraviolet by photographic method, and then removing the unexposed portion with a developing solution such as an alkaline aqueous solution, Further, unnecessary organic components of the photosensitive resin layer containing the phosphor in the exposed portion are removed by baking, and a phosphor pattern is formed only in a necessary portion.

Therefore, when forming the phosphor pattern in the space of the PDP substrate, it is not necessary to confirm the dispersibility of the phosphor, and the storage stability is lower than that of the phosphor dispersion slurry or paste. Are better. Furthermore, since a photographic method is used, a phosphor pattern can be formed with high accuracy.

However, in the conventional method, when the phosphor is collected and reused, the first color is blue, the second color is red, and the third color is green, in consideration of the price of the phosphor. Were sequentially formed. However, when these phosphors are collected for reuse, the color difference changes because the phosphor embedded in the cell immediately before is mixed with the phosphor embedded next.

[0013]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for collecting and reusing a phosphor, even if a phosphor embedded in a cell immediately before is mixed into the collected phosphor. An object of the present invention is to provide a method of manufacturing a phosphor pattern that can produce a phosphor pattern having no color difference change with a high yield.

Another object of the present invention is to provide a phosphor pattern having no color difference change.

Another object of the present invention is to provide a CRT display, a field emission display, a fluorescent display, a radio wave display and a back panel for a plasma display panel having a phosphor pattern having no color difference change.

[0016]

According to the present invention, a multicolor phosphor pattern is formed on a substrate by repeating a photolithography method for each color on a photosensitive resin composition containing a phosphor (A) having a different color. The present invention relates to a method for manufacturing a phosphor pattern, comprising sequentially forming a red phosphor pattern for a first color, a blue color for a second color, and a green phosphor pattern for a third color.

The present invention also relates to a phosphor pattern manufactured by the method for manufacturing a phosphor pattern.

The present invention also provides a CRT display comprising the above-described phosphor pattern on a CRT substrate, a field emission display substrate, a fluorescent display panel substrate, a radio wave emitting display substrate or a plasma display panel substrate. The present invention relates to a back plate for a field emission display, a fluorescent display, a radio-emitting display, or a plasma display panel.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The phosphor pattern of the present invention is obtained by repeating a photolithography method for each color on a photosensitive resin composition containing a phosphor (A) having a different color to form a multicolor phosphor pattern on a substrate. In the method of manufacturing a phosphor pattern to be formed in the first color, the phosphor pattern is formed by sequentially forming a red phosphor pattern in a first color, a blue color in a second color, and a green phosphor pattern in a third color.

In the present invention, the phosphor pattern includes an organic polymer binder, a curing agent having a functional group such as a vinyl group, a hydroxyl group, a carboxyl group, an epoxy group, or an amino group, an organic substance such as an organic solvent, and a phosphor. It is included as an essential component.

This phosphor pattern can be formed by applying a paste containing the above-described components in a pattern on a substrate for a plasma display by a screen printing method, a gravure coating method, or the like, heating and drying and curing as necessary. .

From the viewpoint of obtaining a high-definition pattern shape, the paste containing the above components is used as a photosensitive paste obtained by adding a phosphor to a photoresist, and the phosphor pattern is formed by applying a photolithography method thereto. Can be formed.

Further, from the viewpoints of higher definition pattern shape, phosphor forming property on barrier rib wall surface, and workability, a dry film (photosensitive element) having a photosensitive resin composition layer containing a phosphor is used. This is laminated on a substrate for a plasma display panel, and a phosphor pattern can be formed by applying a photolithography method.

When a phosphor pattern is formed by a photolithography method using a photosensitive resin composition containing phosphors of different colors, the phosphor is converted from the photosensitive resin composition containing the phosphor removed by development. If it is to be recovered and reused, it is inevitable that the fluorescent material of another color used immediately before is mixed into the fluorescent material to be recovered.

For example, when 10% by weight of a red or blue phosphor is mixed into a green phosphor, there is no change in color difference. However, the green and blue phosphors are each 1% by weight based on the red phosphor.
The color difference changes when the above or when the total amount of the green and blue phosphors is 1% by weight or more. In addition, when 5% by weight or more of the green phosphor is mixed with the blue phosphor, the color difference changes.

When a different color is mixed into the phosphor of each color, the upper limit of the mixed amount of the phosphor without a color difference change is when the red or blue phosphor is 10% by weight or less of the green phosphor, or This is when the total amount of the green phosphor is 5% by weight or less. The red phosphor is 10% by weight based on the blue phosphor.
There is no color difference change in the following cases. 9 (a), 9 (b) and 9 (c) show the color difference with respect to the mixing ratio of each color. Note that FIG.
Indicates the color difference when each phosphor is excited using ultraviolet light of 172 nm.

In the present invention, since the phosphor patterns of red for the first color, blue for the second color, and green for the third color are sequentially formed, the collected phosphor is used when the phosphor is collected and reused. Even if the phosphor of the immediately preceding color is mixed therein, the chromaticity does not change, and a phosphor pattern with good color purity can be obtained.

The phosphor used in the present invention is not particularly limited, and a phosphor mainly composed of a usual metal oxide can be used.

As a red-colored phosphor, for example, Y ₂
O ₂ S: Eu, 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.

As a green-colored phosphor, for example, Zn
S: Cu, Zn_TwoSiO_Four: Mn, ZnS: Cu + Zn_Two
SiO_Four: Mn, Gd_TwoO_TwoS: Tb, Y_ThreeAl_FiveO₁₂: C
e, ZnS: Cu, Al, Y_TwoO_TwoS: Tb, ZnO: Z
n, ZnS: Cu, Al + In _TwoO_Three, LaPO_Four: C
e, Tb, BaO.6Al_TwoO_Three: Mn and the like.

As the phosphor emitting blue light, for example, Zn
S: Ag, ZnS: Ag, Al, ZnS: Ag, Ga,
Al, ZnS: Ag, Cu, Ga, Cl, ZnS: Ag
+ In ₂ O ₃ , Ca ₂ B ₅ O ₉ Cl: Eu ²⁺ , (Sr, C
a, Ba, Mg) ₁₀ (PO ₄ ) ₆ C ₁₂ : Eu ²⁺ , Sr ₁₀
(PO ₄ ) ₆ Cl ₂ : Eu ²⁺ , BaMgAl ₁₀ O ₁₇ : Eu
²⁺ , BaMgAl ₁₄ O ₂₃ : Eu ²⁺ , BaMgAl
₁₆ O ₂₆ : Eu ^{2+ and the} like.

In the present invention, the particle size of the phosphor is from 0.1 to 0.1.
It is preferably 20 μm, more preferably 1 to 15 μm, 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 in the present invention is preferably spherical, and the surface area is preferably small.

The photosensitive resin composition containing a phosphor in the present invention is not particularly limited in composition, and can be constituted by using a photosensitive resin composition usually used in a photolithography method. From the viewpoint of workability, (a) a film-imparting polymer, (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group, (c) a photoinitiator that generates free radicals by irradiation with active light, and (d) ) It is preferable to include a phosphor.

(A) As the film-imparting polymer,
A vinyl copolymer is preferable, and as a vinyl monomer used for the vinyl copolymer, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, Ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, iso-propyl acrylate, iso-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, iso-methacrylate Butyl, sec-butyl acrylate, sec-butyl methacrylate, tert-acrylate
-Butyl, tert-butyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, heptyl acrylate, heptyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate,
Octyl methacrylate, nonyl acrylate, nonyl methacrylate, decyl acrylate, decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, octadecyl acrylate, methacrylic acid Octadecyl, eicosyl acrylate, eicosyl methacrylate, docosyl acrylate, docosyl methacrylate, cyclopentyl acrylate, cyclopentyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, cycloheptyl acrylate, cycloheptyl methacrylate, benzyl acrylate, benzyl methacrylate Benzyl, phenyl acrylate, phenyl methacrylate, methoxyethyl acrylate, methacrylate Shiechiru, methoxy acrylic acid diethylene glycol methacrylate methoxy diethylene glycol, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate,
Methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate, acrylic acid 2-
Hydroxyethyl, 2-hydroxyethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, 2-chloroethyl acrylate, Methacrylic acid 2
-Chloroethyl, 2-fluoroethyl acrylate, 2-fluoroethyl methacrylate, 2-cyanoethyl acrylate, 2-cyanoethyl methacrylate, styrene, α-
Examples include methylstyrene, vinyltoluene, vinyl chloride, vinyl acetate, N-vinylpyrrolidone, butadiene, isoprene, chloroprene, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile and the like. These are used alone or in combination of two or more.

Examples of the polymer (a) for imparting film properties include polyvinyl alcohol-based resins (polyacrylate or polymethacrylate hydrolyzate, polyvinyl acetate hydrolyzate, copolymer of ethylene and vinyl acetate). Combined hydrolysate, hydrolyzate of copolymer of ethylene and acrylate, hydrolyzate of copolymer of vinyl chloride and vinyl acetate, copolymer of styrene and acrylate or methacrylate A hydrolyzate of a copolymer of vinyl toluene and an acrylate or methacrylate), a water-soluble salt of carboxyalkyl cellulose, a water-soluble cellulose such as hydroxypropyl cellulose, a water-soluble cellulose ether, Water-soluble salts of carboxyalkyl starch, polyvinylpyrrolidone, etc. It can also be used.

(A) The weight average molecular weight of the film imparting polymer is preferably from 5,000 to 300,000, more preferably from 20,000 to 150,000. 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 (unnecessary portions are easily developed by development). Tend to be reduced).

The weight average molecular weight is a value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve.

Further, the (a) carboxyl group content (acid value (mg) of the film-imparting polymer is so set that the photosensitive resin composition containing the phosphor can be developed with a developer.
KOH / g) can be appropriately adjusted.

For example, when developing with an aqueous alkali solution such as sodium carbonate or potassium carbonate, the acid value is preferably set to 90 to 260. This acid value is
If it is less than 90, development tends to be difficult, and if it exceeds 260, resistance to developing solution (the property that the remaining pattern that is not removed by development and remains as a pattern is not attacked by the developing solution).
Tends to decrease.

When the development is carried out using an aqueous developer comprising water or an aqueous alkali solution and one or more organic solvents, the acid value is preferably from 16 to 260. If the acid value is less than 16, development tends to be difficult,
If it exceeds 260, the developer resistance tends to decrease.

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

As the photopolymerizable unsaturated compound (b) having an ethylenically unsaturated group, all compounds conventionally known as photopolymerizable polyfunctional monomers can be used.

For example, the following general formula (I)

[0044]

Embedded image [Wherein, R represents a hydrogen atom or a methyl group, and k represents 1 to 1
And Y is an integer of 0, and Y is a saturated or unsaturated hydrocarbon residue or a heterocyclic residue or a polyalkylene glycol residue which may have a substituent;

[0045]

Embedded image (Wherein R ¹ and R ² represent a hydrogen atom, a methyl group, an ethyl group,
A propyl group or a trifluoromethyl group is shown, R ³ and R ⁴ are an alkylene group having 1 to 6 carbon atoms, and m and n are each independently an integer of 1 to 20. ). And the like.

In the general formula (I), examples of the saturated or unsaturated hydrocarbon residue or heterocyclic residue optionally having a substituent represented by Y include a halogen atom, a hydroxyl group and an amino group. A straight-chain, branched or alicyclic alkane residue having 1 to 22 carbon atoms which may have a substituent such as a carboxyl group (methane residue, ethane residue, propane residue,
Cyclopropane residue, butane residue, isobutane residue, cyclobutane residue, pentane residue, isopentane residue, neopentane residue, cyclopentane residue, hexane residue,
Cyclohexane residue, heptane residue, cycloheptane residue, octane residue, nonane residue, decane residue, etc.), aromatic ring residue (benzene residue, naphthalene residue, anthracene residue, biphenyl residue, Phenyl residue), heterocyclic residue (furan residue, thiophene residue, pyrrole residue,
Oxazole residue, thiazole residue, imidazole residue, pyridine residue, pyrimidine residue, pyrazine residue, triazine residue, quinoline residue, quinoxaline residue and the like.

Specifically, examples of the photopolymerizable unsaturated compound having one ethylenically unsaturated group include acrylic acid or methacrylic acid ester monomers (methyl acrylate, methyl methacrylate, ethyl acrylate, Ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, iso-propyl acrylate, iso-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, iso-methacrylate Butyl, sec-butyl acrylate, sec-butyl methacrylate, tert-acrylate
-Butyl, tert-butyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, heptyl acrylate, heptyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate,
Octyl methacrylate, nonyl acrylate, nonyl methacrylate, decyl acrylate, decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, octadecyl acrylate, methacrylic acid Octadecyl, eicosyl acrylate, eicosyl methacrylate, docosyl acrylate, docosyl methacrylate, cyclopentyl acrylate, cyclopentyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, cycloheptyl acrylate, cycloheptyl methacrylate, benzyl acrylate, benzyl methacrylate Benzyl, phenyl acrylate, phenyl methacrylate, methoxyethyl acrylate, methacrylate Siethyl, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, 2-chloroethyl acrylate, 2-chloroethyl methacrylate, 2-fluoroethyl acrylate, 2-fluoro methacrylate Ethyl, acrylic acid 2
-Cyanoethyl, 2-cyanoethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, etc.), styrene Monomer (styrene, α-methylstyrene, pt-butylstyrene, etc.), polyolefin monomer (butadiene, isoprene, chloroprene, etc.), vinyl monomer (vinyl chloride, vinyl acetate, etc.), nitrile monomer (acrylonitrile, methacrylic acid) Lonitrile), 1- (methacryloyloxyethoxycarbonyl) -2- (3'-chloro-2'-hydroxypropoxycarbonyl) ben Down (.gamma.-chloro -β- hydroxypropyl -β'- methacryloyloxyethyl -o- phthalate) and the like.

Examples of the photopolymerizable unsaturated compound having two ethylenically unsaturated groups include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, and triethylene glycol diacrylate. Methacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, hexapropylene glycol diacrylate, hexapropylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, butylene glycol diacrylate , Butylene Recall dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate,
1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,5-pentanediol diacrylate, 1,5-pentanediol dimethacrylate, 1,6-hexanediol diacrylate,
1,6-hexanediol dimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, trimethylolpropane dimethacrylate, trimethylolpropane dimethacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, 2,2-bis (4-acrylic Roxyethoxyphenyl) propane, 2,2-bis (4-methacryloxyethoxyphenyl) propane, 2,2-bis (4-acryloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloxydiethoxyphenyl) )propane,
2,2-bis (4-acryloxypolyethoxyphenyl) propane, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, Y in the formula (I)
But

[0049]

Embedded image (Wherein m and n are each independently an integer from 1 to 20), bisphenol A diglycidyl ether diacrylate, bisphenol A diglycidyl ether dimethacrylate, urethane diacrylate compound, and the like.

Examples of the photopolymerizable unsaturated compound having three ethylenically unsaturated groups include, for example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, and ethylene oxide-modified trimethylol. Examples include propane triacrylate, ethylene oxide-modified trimethylolpropane trimethacrylate, trimethylolpropane triglycidyl ether triacrylate, and trimethylolpropane triglycidyl ether trimethacrylate.

Examples of the photopolymerizable unsaturated compound having four ethylenically unsaturated groups include tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol tetraacrylate, and pentaerythritol tetramethacrylate.

Examples of the photopolymerizable unsaturated compound having five ethylenically unsaturated groups include dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate and the like.

Examples of the photopolymerizable unsaturated compound having six ethylenically unsaturated groups include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate and the like.

Any of these photopolymerizable unsaturated compounds having an ethylenically unsaturated group may be those capable of undergoing radical polymerization upon irradiation with light. The sexually unsaturated compounds are used alone or in combination of two or more.

Further, the photosensitive resin composition containing the phosphor in the present invention needs to be removed by baking during the formation of the phosphor pattern.
Among the photopolymerizable unsaturated compounds having an ethylenically unsaturated group, polyethylene glycol dimethacrylate having good thermal decomposability is more preferably used.

Further, when the photosensitive resin composition layer containing the phosphor is formed using a photosensitive element having a buried layer, the storage stability after embedding in the space of the PDP substrate is improved. (B) the photopolymerizable unsaturated compound having an ethylenically unsaturated group in the containing photosensitive resin composition layer can suppress migration of the ethylenically unsaturated group into the burying layer) and a phosphor-containing photosensitive resin composition (B) in the photosensitive resin composition containing the phosphor during heating under reduced pressure when embedding the layer in the space of the PDP substrate
From the viewpoint that the evaporation of the photopolymerizable unsaturated compound having an ethylenically unsaturated group can be suppressed, the weight average molecular weight of (b) the photopolymerizable unsaturated compound having an ethylenically unsaturated group is 400.
The boiling point (760 mmHg) of the photopolymerizable unsaturated compound (b) having an ethylenically unsaturated group is preferably at least 500, more preferably at least 500, particularly preferably at least 600. The temperature may be 300 ° C. or higher, and there is no particular limitation. From the viewpoint of stability and workability when heated under reduced pressure, the boiling point (760 mmH
g) is preferably 350 ° C. or more, and 400 ° C.
More preferably, it is the above.

(B) a photopolymerizable compound having an ethylenically unsaturated group having a weight average molecular weight of 400 or more, or (b) a photopolymerizable compound having an ethylenically unsaturated group having a boiling point (760 mmHg) of 300 ° C. or more As the unsaturated compound, for example, the photopolymerizable unsaturated compound can be selected and used.

Since it is necessary to remove unnecessary components by baking when forming a phosphor pattern described later, of the photosensitive resin composition constituting the photosensitive resin composition containing the phosphor of the present invention, Since the photosensitive resin composition other than the phosphor and the binder described below used as necessary needs to have good thermal decomposability, carbon, hydrogen, oxygen and It is preferable not to include anything other than nitrogen.

(C) Examples of photoinitiators that generate free radicals upon irradiation with actinic light include aromatic ketones (benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-
Methoxy-4'-dimethylaminobenzophenone, 2-
Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- (4-
(Methylthio) phenyl) -2-morpholinopropanone-1,2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,4-diethylthioxanthone, 2- Ethyl anthraquinone, phenanthrenequinone, etc.), benzoin ether (benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, etc.),
Benzoin (methylbenzoin, ethylbenzoin, etc.), benzyl derivative (benzyldimethylketal, etc.), 2,4,5-triarylimidazole dimer (2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,
5-di (m-methoxyphenyl) imidazole dimer,
2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl)-
4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, -(2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer and the like, and acridine derivatives (9-phenylacridine,
1,7-bis (9,9'-acridinyl) heptane and the like
And the like. These are used alone or in combination of two or more.

(D) As described above, the phosphor is used.

The amount of the component (a) in the present invention is as follows:
The total amount of the component (a) and the component (b) is preferably 10 to 90 parts by weight based on 100 parts by weight, and more preferably 20 to 8 parts by weight.
More preferably, it is 0 parts by weight. If this blending amount is 1
If it is less than 0 parts by weight, when the photosensitive element is supplied in the form of a roll, the photosensitive resin composition containing the phosphor oozes out from the end of the roll (hereinafter, referred to as edge fusion), so that when the photosensitive element is laminated, Dispensing from a roll becomes difficult, and the extruded portion is partially and excessively buried in the space of the PDP substrate, causing a problem such as a remarkable decrease in manufacturing yield and a tendency such as a decrease in film formability. When the amount exceeds 90 parts by weight, the sensitivity tends to be insufficient.

The amount of the component (b) in the present invention is as follows:
The total amount of the component (a) and the component (b) is preferably 10 to 90 parts by weight based on 100 parts by weight, and more preferably 20 to 8 parts by weight.
More preferably, it is 0 parts by weight. If this blending amount is 1
If the amount is less than 0 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 the photosensitive element and In such a case, the photosensitive resin composition containing the phosphor tends to exude from the edge due to the flow, and the film-forming property tends to decrease.

The amount of the component (c) in the present invention is as follows:
The amount is preferably 0.01 to 30 parts by weight based on 100 parts by weight of the total of the components (a) and (b).
More preferably, it is 1 to 20 parts by weight. If the amount is less than 0.01 part by weight, the sensitivity of the photosensitive resin composition containing the phosphor tends to be insufficient. If 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 the component (d) in the present invention is as follows:
The amount is preferably from 10 to 500 parts by weight, more preferably from 10 to 400 parts by weight, based on 100 parts by weight of the total of the components (a), (b) and (c).
It is particularly preferred that the content be 0 to 300 parts by weight,
It is extremely preferred to be 50 parts by weight. When the compounding amount is less than 10 parts by weight, the luminous efficiency tends to decrease when light is emitted as a PDP, and when it exceeds 500 parts by weight, when a photosensitive element is used, the film formability decreases, Flexibility tends to decrease.

The photosensitive resin composition according to the present invention does not cause thickening 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, saturated fatty acids, unsaturated fatty acids, aliphatic dibasic acids,
Examples thereof include aromatic dibasic acids, aliphatic tribasic acids, and aromatic tribasic acids.

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 from the viewpoint 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 10 parts by weight, the effect of storage stability tends to decrease, and if it exceeds 30 parts by weight, sensitivity tends to be insufficient.

It is preferable to add a dispersant to the photosensitive resin composition of the present invention in order to improve the dispersion of the phosphor.

As dispersants, inorganic dispersants (silica gel, bentonite, kaolinite, talc, hectorite, montmorillonite, saponite, beidellite, etc.) and organic dispersants (aliphatic amide, fatty amide, etc.) Group-based esters, polyethylene oxides, sulfate ester-based anionic surfactants, polycarboxylic acid amine salts, polycarboxylic acids, polyamides, polymer polyethers, acrylic copolymers, special silicones, etc.) Can be
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, the pattern formation accuracy (the property of obtaining a pattern formed of a photosensitive resin composition layer containing a phosphor, which is dimensionally accurate and in a desired shape after development) tends to decrease. .

It is preferable to use a binder in the photosensitive resin composition of the present invention in order to prevent the phosphor from peeling off the PDP substrate after firing.

As the binder, for example, low melting glass,
Metal alkoxides, silane coupling agents and the like can be mentioned. 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.

The photosensitive resin composition of the present invention requires a dye, a color former, a plasticizer, a pigment, a polymerization inhibitor, a surface modifier, a stabilizer, an adhesion promoter, a thermosetting agent, and the like. It can be added accordingly.

In the present invention, an alkali developer is preferably used as a developer used in the photolithography method. Examples of the base of the alkali developer include alkali hydroxides (such as hydroxides of lithium, sodium or potassium), alkali carbonates (such as carbonates or bicarbonates of lithium, sodium or potassium), and alkali metal phosphates (such as phosphoric acid). Potassium, sodium phosphate, etc.), alkali metal pyrophosphates (sodium pyrophosphate, potassium pyrophosphate, etc.), tetramethylammonium hydroxide, triethanolamine, etc., among which sodium carbonate, tetramethylammonium hydroxide, etc. Preferred are mentioned.

The pH of the aqueous alkali solution used for development is 9
To 11, and the temperature can be adjusted according to the developability.

Further, a surfactant, an antifoaming agent, and a small amount of an organic solvent for accelerating the development can be mixed in the aqueous alkali solution.

When the phosphor pattern is formed by applying a photolithography method in which a photosensitive resin composition containing a phosphor is subjected to wet development using an alkali developing solution,
The phosphor is peeled off from the cell by the alkali development, and the phosphor remains in the developer tank. When this phosphor is collected and used again for pattern formation, it is preferable to subject the phosphor to acid treatment or water washing (neutralization treatment) before pattern formation. In order to suppress a decrease in emission luminance or a change in color difference of the phosphor, the content of the alkali metal or alkaline earth metal in the phosphor is preferably set to 2% by weight or less (based on 1 g of the phosphor). . As this method, acid treatment or water washing (neutralization treatment) is effective. This acid treatment or water washing (neutralization treatment) is preferably performed using an organic acid, an inorganic acid or an aqueous solution of these acids or water alone at a temperature of 10 to 80 ° C. for 1 to 180 minutes. Base is removed. In addition, the phosphor is separated from the above-mentioned organic acid, inorganic acid, aqueous solution or water thereof at a temperature of 10 to 80 ° C. by a known method such as filtration, centrifugation, or natural sedimentation.

Examples of the acid for acid-treating the phosphor 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 are exemplified.

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, aspartic acid, azelaic acid, anisic acid, metanylic acid, sulfanilic acid , Anthranilic acid, 2-aminoethylsulfonic acid, 4-aminobutyric acid, benzoic acid, isonicotinic acid, methyl isonicotinate, 2-indolecarboxylic acid, oxaloacetic acid, glyoxylic acid, glycolic acid, glycerin phosphate, glucose-1 -Phosphoric acid, reduced glutathione, Tamic acid, glutaric acid, chlorobenzoic acid, 2-chloropropionic acid, cinnamic acid, salicylic acid, sarcosine, cyanobenzoic acid, 2,4-diaminobutyric acid, dichloroacetic acid, N, N-dimethylglycine, penicillamine, tartaric acid, thioic acid Glycolic acid, trichloroacetic acid,
Naphthoic acid, nitrobenzoic acid, lactic acid, barbituric acid, picric acid, picolinic acid, hydroxybenzoic acid, vinylacetic acid, 2,6-pyridinedicarboxylic acid, phenylacetic acid, fumaric acid, 2-furancarboxylic acid, fluorobenzoic acid, fluoro Acetic acid, bromobenzoic acid, hexafluoroacetylacetone, phthalic acid, mandelic acid, mercaptoacetic acid, iodobenzoic acid, iodoacetic acid, levulinic acid and the like can be mentioned. Specific examples of the inorganic acid include sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid.

Of these, from the point of high neutralization effect,
Formic acid, oxalic acid, malonic acid, citric acid, tartaric acid, lactic acid,
Preferred are those having a dissociation index pKa of 0.1 to 7 in an aqueous solution of picric acid, fumaric acid, phthalic acid, maleic acid, mandelic acid, or the like. These may be used alone or in combination of two or more.

The pH of the aqueous acid solution used for this acid treatment is 1
The pH and temperature of the aqueous acid solution can be adjusted in accordance with the acid resistance of the phosphor (durability that does not deteriorate with acid). Further, after the acid treatment (neutralization treatment), a step of washing with water can be performed.

Hereinafter, an example of a method for manufacturing a phosphor pattern according to the present invention will be described with reference to FIG. FIG. 1 is a schematic view showing each step of an example of a method for producing a phosphor pattern of the present invention, wherein 1 is a substrate, 2 is a barrier rib, 5 is a photosensitive resin composition layer, and 5 ′ is a light. The cured photosensitive resin composition layer, 6 is a buried layer, 8 is a photomask, 9 is an actinic ray, and 10 is a phosphor pattern.

[(I) Step of Forming Photosensitive Resin Composition Layer Containing Phosphor on Substrate Having Irregularities] The photosensitive resin composition layer containing a phosphor in the present invention is a liquid photosensitive resin composition. Alternatively, it is formed on an uneven surface of a substrate having unevenness using a photosensitive element. The method of forming is not particularly limited, for example, by dissolving or mixing each component constituting the above-described photosensitive resin composition in a dissolvable or dispersible solvent to obtain a liquid that is uniformly dispersed. A method in which a paste is directly applied to an uneven surface and formed by drying, a method in which a paste is formed on the uneven surface by using a photosensitive element having a photosensitive resin composition layer containing a phosphor, and the like. .

Examples of the substrate having irregularities in the present invention include a substrate for a plasma display panel (substrate for PDP) on which barrier ribs are formed.

Examples of the PDP substrate include a substrate made of a glass plate, a synthetic resin or the like, 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.

The method for forming these on a substrate is not particularly limited. For example, electrodes can be formed on a substrate by a method such as vapor deposition, sputtering, plating, coating, printing, and the like. Barrier ribs can be formed by a method such as sandblasting or embedding.

FIGS. 2 and 3 show a P having a barrier rib formed thereon.
A schematic diagram of the DP substrate is shown. The barrier ribs usually have a height of 20 to 500 μm and a width of 20 to 200 μm. 2 and 3, reference numeral 3 denotes a grid-shaped discharge space, and 4 denotes a stripe-shaped discharge space.

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, etc., and is usually shown in FIGS. Such a grid-like or stripe-like discharge space is formed.

2 and 3, a barrier rib 2 is formed on a substrate 1. In FIG.
However, in FIG. 3, a stripe-shaped discharge space 4 is formed. The size of the discharge space is determined by the size and resolution of the PDP. Generally, in the case of a grid-like discharge space as shown in FIG. 2, the vertical and horizontal lengths are 50 μm to 1 mm, and the stripe as shown in FIG. In case of a discharge space, the interval is 3
0 μm to 1 mm. FIGS. 4 and 5 show two aspects of the state of the PDP substrate after the completion of this step.

[(II) Step of irradiating the photosensitive resin composition layer containing the phosphor imagewise with actinic rays] The state of irradiating actinic rays 9 imagewise is shown in FIG. 1 (II). FIG. 1 (I
In the method (I), the actinic ray 9 is imagewise irradiated by a method in which a photomask 8 such as a negative film or a positive film is provided on the photosensitive resin composition layer 5 in the state shown in FIG. The actinic ray 9 can be irradiated imagewise.

At this time, on the photosensitive resin composition layer 5,
The above-mentioned support film is newly coated and actinic rays 9
Can be illuminated imagewise.

If the buried layer 6 is made of a material that transmits the actinic ray 9, this step may be performed in a state where the buried layer 6 is disposed, and then a step of removing the buried layer 6 may be performed. it can.

The transmission width of the actinic rays 9 of the photomask 8 is usually the opening width of the concave portion of the PDP substrate. However, in the case of laminating as shown in FIG. A photosensitive resin containing an undesired photocured phosphor on a barrier rib may have a transmission width equal to the opening width of the concave portion of the PDP substrate or a transmission width smaller than the opening width of the concave portion of the PDP substrate. This is preferable because the tolerance of the positioning accuracy can be increased without leaving the composition.

As the actinic ray 9, 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 range, 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. In addition, a photo flood bulb, 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.

[0100] The irradiation of active light 9 in the present invention is not particularly limited, preferably in the 5~10000mJ / cm ^2, more preferably to 7~5000mJ / cm ^2, 10~1000mJ / Cm ² is particularly preferred.

[(III) Step of selectively removing unnecessary portions of the photosensitive resin composition layer containing the phosphor which has been image-irradiated with actinic rays by development to form a pattern] Unnecessary portions are removed by development FIG. 1 (III) shows the state after the completion. In FIG. 1 (III), 5 ′ is a photosensitive resin composition layer after photo-curing.

In the step of FIG. 1 (III), for example, if the support film is present on the photosensitive resin composition layer 5 after the state of FIG. After removing, aqueous alkaline solution, aqueous developer,
A method of performing development by a known method such as spraying, rocking immersion, brushing, and scrubbing using a known developer such as an organic solvent to remove unnecessary portions, and the like.

As a method for removing unnecessary portions of the photosensitive resin composition 5, the difference between the adhesiveness of the exposed portion and the unexposed portion is utilized, and only the unnecessary portion of the photosensitive resin composition 5 having the adhesiveness is used. Can be carried out by dry development for peeling off.

Examples of the base of the aqueous alkali solution include alkali hydroxides (such as hydroxides of lithium, sodium or potassium), alkali carbonates (such as carbonates or bicarbonates of lithium, sodium or potassium), and alkali metal phosphates (such as carbonates or bicarbonates). Potassium phosphate, sodium phosphate, etc.), alkali metal pyrophosphates (sodium pyrophosphate, potassium pyrophosphate, etc.), tetramethylammonium hydroxide, triethanolamine, etc., among which sodium carbonate, tetramethylammonium hydroxide And the like are preferred.

The pH of the aqueous alkali solution used for development is 9
To 11, and the temperature can be adjusted according to the developability of the photosensitive resin composition layer 5.

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 aqueous alkali solution,
Other than the above substances, for example, borax, sodium metasilicate, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,
3-propanediol, 1,3-diaminopropanol-2-morpholine, tetramethylammonium hydroxide 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 alcohol, 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, and diethylene glycol. Monobutyl ether and the like. These are used alone or in combination of two or more.

A water-based 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 1. 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 monomethyl ether, dipropylene glycol monopropyl ether, 3-methyl-3-methoxybutyl acrylate, 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cycle Hexanone, methyl isobutyl ketone, .gamma.-butyrolactone. These are used alone or in combination of two or more.

The concentration of the organic solvent is usually 2 to 90% by weight.
The temperature can be adjusted according to the developing property.

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, γ-butyrolactone, and the like. 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 at least one organic solvent or an aqueous alkali solution and at least one organic solvent), and an organic solvent 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.

After the development, in order to improve the adhesiveness and chemical resistance of the photo-cured photosensitive resin composition layer 5 ′ on the inner surface of the concave portion on the PDP substrate, ultraviolet irradiation by a high-pressure mercury lamp or the like is performed. Heating can also be performed.

At this time, the irradiation amount of ultraviolet rays is usually 0.2
Ｊ10 J / cm ² , and heating can be performed during irradiation. Further, the heating temperature is preferably from 60 to 180 ° C, more preferably from 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.

In the case where the photosensitive resin composition layer 5 containing a phosphor exists above the projections as shown in FIG. 5, this process may be performed depending on the exposure / development conditions and the misalignment of the photomask. By performing the (III) step, the photosensitive resin composition layer (unnecessary part) containing the phosphor after photocuring remaining on the inner surface of the concave portion tends to remain. In this case, unnecessary portions of the photo-cured photosensitive resin composition layer 5 ′ remaining on portions other than the inner surfaces of the concave portions can be completely removed by polishing or the like.

Further, assuming such a case, after forming a multicolor pattern made of a photosensitive resin composition containing a phosphor that emits red, blue, and green, which will be described later, and before forming a firing step described later, Applying or printing a black inorganic material paste including a black inorganic pigment such as iron oxide, chromium oxide, and copper oxide and a low-melting glass frit on the convex portion, or forming a black stripe using a black inorganic material-containing photosensitive element. After formation, baking described below can be performed.

[Step (IV) of recovering and reusing the phosphor dropped from the pattern into the developer tank in the steps (IV) and (III)] The method of recovering the phosphor of the present invention from the developer tank is not particularly limited. Instead, for example, a known method such as filtration, centrifugation, or natural sedimentation is used to separate the phosphor from the developer.

Further, the base of the aqueous alkali solution remaining on the phosphor can be subjected to an acid treatment or a water washing (neutralization treatment) using an organic acid, an inorganic acid or an aqueous solution of these acids or water.

Specific acids include, for example, saturated fatty acids, unsaturated fatty acids, aliphatic dibasic acids, aromatic dibasic acids,
Organic acids and inorganic acids such as aliphatic tribasic acids and aromatic tribasic acids are exemplified.

The pH of the aqueous acid solution used for the acid treatment is 2-6.
Preferably, the pH and temperature of the aqueous acid solution can be adjusted according to the acid resistance of the phosphor (durability that does not deteriorate with acid).

By the acid treatment, a phosphor having an alkali metal or alkaline earth metal content of 20 mg (2% by weight) or less based on 1 g of the phosphor can be obtained.

Further, after the acid treatment (neutralization treatment), a step of washing with water can be performed.

[(IV) Step of Removing Unwanted Parts by Firing] FIG. 1 (IV) shows a state in which the phosphor pattern has been formed after the unnecessary parts have been removed by firing. FIG. 1 (I
In V), 10 is a phosphor pattern.

In FIG. 1 (IV), the firing method is not particularly limited, and a known firing method may be used to remove unnecessary components other than the phosphor and the binder to form a phosphor pattern. it can.

The firing temperature at this time is 350 to 800 ° C.
And more preferably 400 to 600 ° C. 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. Before reaching the maximum firing temperature,
A step of holding the temperature between 450 ° 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 from the viewpoint that the number of steps can be reduced.
After forming a multicolor pattern composed of a photosensitive tree composition layer containing a phosphor that emits red, blue and green light, (I
It is preferable to perform the step V) to form a multicolor phosphor pattern.

[0131] Each of the steps (I) to (III) in the present invention is repeated for each color to form a pattern of a photosensitive tree composition containing a phosphor that emits red, blue and green light. 6 is shown. In FIG. 6, 5'a is a first color pattern, 5'b is a second color pattern, and 5'c is 3
It is a color pattern.

FIG. 7 shows a state in which a multicolor phosphor pattern is formed. 10a is a first phosphor pattern, 10b is a second phosphor pattern, and 10c 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 to repeat the steps (IV) in the order of red, blue and green to form a multicolor phosphor pattern that emits red, blue and green.

The back plate for a plasma display panel of the present invention is obtained by combining the phosphor pattern obtained as described above with
It is provided on a plasma display panel substrate.

The back plate for a plasma display panel will be described below with reference to FIG. In addition, FIG.
FIG. 9 is a schematic view showing an example of a plasma display panel (PDP). In FIG. 8, 1 is a substrate, 2 is a barrier rib, 4 is a stripe-shaped discharge space, 10 is a phosphor pattern, 11 is an address electrode, and 12 is a protective film. , 13 is a dielectric layer, 14 is a display electrode, and 15 is a front plate substrate.

In FIG. 8, the lower portion including the substrate 1, the barrier ribs 2, the phosphor pattern 10, and the address electrodes 11 is the back plate for the PDP, and the protective film 12, the dielectric layer 13, the display electrodes 14, and the front plate. The upper part including the substrate 15 is a PDP
It is a front plate for use.

PDPs can be classified into ΔC (alternating current) type PDPs, DC (direct current) type PDPs, and the like according to the voltage application method, and the schematic diagram of FIG. 8 shown as an example is a ΔC type PDP.

The method of manufacturing a phosphor pattern according to the present invention employs a field emission display (FED),
The present invention can be applied to a self-luminous display such as an electroluminescence display (ELD).

In the present invention, a red phosphor for the first color, a blue phosphor for the second color, and a green phosphor pattern for the third color are formed in this order. Even if the phosphor of the immediately preceding color is mixed therein, the chromaticity does not change, and a phosphor with good color purity can be obtained.

[0140]

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

Production Example 1 Preparation of Solution (d-1) of Film-Providing Polymer The materials shown in Table 1 were charged into a flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer. The temperature was raised to 80 ° C. in a nitrogen gas atmosphere, and the materials shown in Table 1 were uniformly dropped over 4 hours while maintaining the reaction temperature at 80 ° C. ± 2 ° C.

After dropping, stirring was continued at 80 ° C. ± 2 ° C. for 6 hours, and the weight average molecular weight was 80,000 and the acid value was 130 mg.
KOH / g of a film-imparting polymer solution (solid content 4
(5.5% by weight) (d-1) was obtained.

[0143]

[Table 1] Production Example 2 [A solution for a photosensitive resin composition layer containing a phosphor (D-
1) Production of the materials shown in Table 2 using a raikai machine
After mixing for 5 minutes, a solution (D-1) for a photosensitive resin composition containing a phosphor was prepared.

[0144]

[Table 2] The solution (D-1) for a photosensitive resin composition containing a phosphor obtained in Production Example 2 was uniformly applied on a polyethylene terephthalate film having a thickness of 20 μm, and a hot air convection dryer at 110 ° C. For 10 minutes to remove the solvent, thereby forming a photosensitive resin composition layer containing a phosphor. The thickness of the photosensitive resin composition layer containing the obtained phosphor is 50 μm.
m.

Then, a polyethylene film having a thickness of 25 μm was further laminated on the photosensitive resin composition layer containing the phosphor as a cover film to produce a photosensitive element (i).

Production Example 3 [Solution for Photosensitive Resin Composition Containing Phosphor (D-2)
Preparation of a phosphor-containing solution for a photosensitive resin composition (D-2) in the same manner as in Production Example 2 except that the materials shown in Table 2 were replaced with the materials shown in Table 3 in Production Example 2 Was prepared.

[0147]

[Table 3] The solution (D-2) for a photosensitive resin composition containing a phosphor obtained in Production Example 3 was uniformly applied on a polyethylene terephthalate film having a thickness of 20 μm, and was heated at 110 ° C. by a hot air convection dryer. For 10 minutes to remove the solvent, thereby forming a photosensitive resin composition layer containing a phosphor. The thickness of the photosensitive resin composition layer containing the obtained phosphor is 50
μm.

Next, a 25 μm-thick polyethylene film was further laminated as a cover film on the phosphor-containing photosensitive resin composition layer to produce a photosensitive element (ii).

Production Example 4 [Solution for photosensitive resin composition containing phosphor (D-3)]
Preparation of a phosphor-containing solution for a photosensitive resin composition (D-3) in the same manner as in Production Example 2 except that the materials shown in Table 2 were replaced with the materials shown in Table 4 in Production Example 2 Was prepared.

[0150]

[Table 4] The solution (D-3) for a photosensitive resin composition containing a phosphor obtained in Production Example 4 was uniformly applied on a polyethylene terephthalate film having a thickness of 20 μm, and a hot air convection dryer at 110 ° C. For 10 minutes to remove the solvent, thereby forming a photosensitive resin material containing a phosphor. The thickness of the photosensitive resin composition layer containing the obtained phosphor was 50 μm.

Next, a 25 μm-thick polyethylene film was further formed on the phosphor-containing photosensitive resin material.
The photosensitive element (iii) was produced by bonding together as a cover film.

[Experimental operation 1] Example 1 A PDP substrate (stripe-shaped barrier ribs, opening width between barrier ribs 140 μm, barrier rib width 70 μm, barrier rib height 140 μm) was formed on the side where barrier ribs were formed. While peeling off the polyethylene film of the photosensitive element (iii) obtained in the above, using a vacuum laminator (trade name: VLM-1 type, manufactured by Hitachi Chemical Co., Ltd.), the heat shoe temperature was 30 ° C. and the laminating speed was 1 .
5 m / min, air pressure 4,000 Pa or less, crimping pressure (cylinder pressure) 5 × 10 ⁴ Pa (thickness 3 mm, length 10 c
Since a substrate of mx 10 cm in width was used, the layers were laminated at a linear pressure of 2.4 x 10 ³ N / m at this time.

Next, the polyethylene terephthalate film on the surface of the photosensitive element (iii) that is not in contact with the barrier rib is peeled off, and a 100 μm-thick polyethylene film (Vicat softening point) is placed on the photosensitive resin composition containing the phosphor. : 82 to 100 ° C.) as the burying layer,
Laminator (HLM-3, manufactured by Hitachi Chemical Co., Ltd.)
000 type), the laminating temperature is 70 ° C., the laminating speed is 0.5 m / min, and the pressing pressure (cylinder pressure)
Is 4 × 10 ⁵ Pa (thickness 3 mm, length 10 cm × width 10
cm substrate, the linear pressure at this time was 9.8 × 1
0 ³ Crimp the buried layer N / m), a photosensitive resin composition containing a phosphor and a buried layer, embedded into a space surrounded by the barrier rib walls and the substrate on the bottom.

Next, the thickness of the buried layer is 100 μm.
An adhesive tape was adhered to the polyethylene film of No. 1, and the embedded layer was physically peeled off.

Next, a photomask for testing was brought into close contact with the surface of the photosensitive element (iii) which was not in contact with the barrier rib, and was exposed to 500 mJ / cm using an HMW-590 type exposure machine manufactured by Oak Manufacturing Co., Ltd. Actinic light was imagewise irradiated in ² and spray-developed at 30 ° C. for 70 seconds using a 1% by weight aqueous solution of sodium carbonate as a developing solution using a developing machine (e-1) to obtain a red phosphor pattern precursor. . At this time, the used developer was centrifuged to separate the red phosphor. Then, the operation of adding water to the separated phosphor, stirring and centrifuging was repeated six times. The pH of the aqueous solution containing the phosphor after this operation was 7.

Next, acetone was added to the separated phosphor and centrifuged to separate the phosphor. Further, water was added to the separated phosphor and centrifuged. Next, the separated phosphor was collected, and the phosphor was dried at 90 ° C. for 24 hours to recover a red phosphor (R-1).

Further, the obtained red phosphor (R-1) was packed in a stainless steel plate having a hole of 2 cm in diameter and 1 mm in thickness, and the color difference was evaluated using a microfluorometer (manufactured by Spectrometer Co., Ltd.). The results are shown in Table 5.

Here, the wavelength for exciting the phosphor is 172 n
m. The untreated and unfired red phosphor was used as a reference for the color difference.

Example 2 In Example 1, the photosensitive element (iii) produced in Production Example 4 was replaced with the photosensitive element (i) produced in Production Example 2, and a PDP substrate was produced in Example 1. In the same manner as in Example 1 except that the respective steps of lamination, exposure, and development (using a developing machine (e-1 ′)) were performed instead of the substrate on which the red phosphor pattern precursor was formed. Thus, the blue phosphor (B-1) was recovered.

Table 5 shows the results of evaluating the color difference of the obtained blue phosphor (B-1). The untreated and unfired blue phosphor was used as a reference for the color difference.

Example 3 In Example 1, the photosensitive element (iii) produced in Production Example 4 was replaced with the photosensitive element (ii) produced in Production Example 3, and a PDP substrate was produced in Example 2. Laminating, exposing, developing (developing machine (e-
1 '') was used. The green phosphor (G-1) was recovered in the same manner as in Example 1 except that each step of (1) was performed.

Table 5 shows the results of evaluating the color difference of the obtained green phosphor (G-1). The untreated and unfired green phosphor was used as a reference for the color difference.

[Experiment 2] Comparative Example 1 In Example 2, the photosensitive element (i) produced in Production Example 2 was replaced with the photosensitive element (i) produced in Production Example 3.
A green phosphor (G-2) was recovered in the same manner as in Example 2 except that i) was replaced.

Table 5 shows the results of evaluating the color difference of the obtained green phosphor (G-2). The untreated and unfired green phosphor was used as a reference for the color difference.

Comparative Example 2 In Example 3, the photosensitive element (ii) produced in Production Example 3 was replaced with the photosensitive element (i) produced in Production Example 2, and red and blue produced in Example 2 were used. Except that the substrate on which the phosphor pattern precursor was formed was replaced with the substrate on which the red and green phosphor pattern precursors prepared in Comparative Example 1 were formed, the same procedure as in Example 3 was repeated, except that the blue phosphor (B- 2) was collected.

Table 5 shows the results of evaluating the color difference of the obtained blue phosphor (B-2). The untreated and unfired blue phosphor was used as a reference for the color difference.

[Experiment 3] Comparative Example 3 Example 1 was repeated except that the photosensitive element (iii) produced in Production Example 4 was replaced with the photosensitive element (ii) produced in Production Example 3. In the same manner as in the above, the green phosphor (G-3) was recovered.

Table 5 shows the results of evaluating the color difference of the obtained green phosphor (G-3). The untreated and unfired green phosphor was used as a reference for the color difference.

Comparative Example 4 In Example 2, the photosensitive element (i) produced in Production Example 2 was replaced with the photosensitive element (ii) produced in Production Example 4.
Example 1 except that i) was replaced and the substrate on which the red phosphor pattern precursor prepared in Example 1 was formed was replaced by the substrate on which the green phosphor pattern precursor prepared in Comparative Example 3 was formed In the same manner as in 2, the red phosphor (R-2) was recovered.

Table 5 shows the results of evaluating the color difference of the obtained red phosphor (R-2). The untreated and unfired red phosphor was used as a reference for the color difference.

Comparative Example 5 In Example 3, the photosensitive element (ii) produced in Production Example 3 was replaced with the photosensitive element (i) produced in Production Example 2, and red and blue produced in Example 2 were used. Except that the substrate on which the phosphor pattern precursor was formed was replaced with the substrate on which the green and red phosphor pattern precursors prepared in Comparative Example 4 were formed, the same procedure as in Example 3 was repeated, except that the blue phosphor (B- 3) was recovered.

Table 5 shows the results of evaluating the color difference of the obtained blue phosphor (B-3). The untreated and unfired blue phosphor was used as a reference for the color difference.

[Experimental operation 4] Comparative example 6 In Example 2, the substrate on which the red phosphor pattern precursor prepared in Example 1 was formed was replaced with the green phosphor pattern precursor produced in Comparative example 3. A blue phosphor (B-4) was recovered in the same manner as in Example 2 except that the substrate was replaced.

Table 5 shows the results of evaluating the color difference of the obtained blue phosphor (B-4). The untreated and unfired blue phosphor was used as a reference for the color difference.

Comparative Example 7 In Example 3, the photosensitive element (ii) produced in Production Example 3 was replaced with the photosensitive element (i) produced in Production Example 4.
ii) and replacing the substrate on which the red and blue phosphor pattern precursors produced in Example 2 were formed with the substrate on which the green and blue phosphor pattern precursors produced in Comparative Example 6 were formed A red phosphor (R-3) was recovered in the same manner as in Example 3 except for the above.

Table 5 shows the results of evaluating the color difference of the obtained red phosphor (R-3). The untreated and unfired red phosphor was used as a reference for the color difference.

[Experiment 5] Comparative Example 8 Example 1 was repeated except that the photosensitive element (iii) produced in Production Example 4 was replaced with the photosensitive element (i) produced in Production Example 2. In the same manner as in the above, the blue phosphor (B-5) was recovered.

Table 5 shows the results of evaluation of the color difference of the obtained blue phosphor (B-5). The untreated and unfired blue phosphor was used as a reference for the color difference.

Comparative Example 9 In Example 2, the photosensitive element (i) produced in Production Example 2 was replaced with the photosensitive element (ii) produced in Production Example 4.
Example 1 except that i) was replaced and the substrate on which the red phosphor pattern precursor produced in Example 1 was formed was replaced by the substrate on which the blue phosphor pattern precursor produced in Comparative Example 8 was formed In the same manner as in 2, the red phosphor (R-4) was recovered.

Table 5 shows the results of evaluating the color difference of the obtained red phosphor (R-4). The untreated and unfired red phosphor was used as a reference for the color difference.

Comparative Example 10 In Example 3, the substrate on which the red and blue phosphor pattern precursors produced in Example 2 were formed was replaced with the substrate on which the blue and red phosphor pattern precursors produced in Comparative Example 9 were formed. The green phosphor (G-4) was recovered in the same manner as in Example 3 except that the above-mentioned was replaced.

Table 5 shows the results of evaluating the color difference of the obtained green phosphor (G-4). The untreated and unfired green phosphor was used as a reference for the color difference.

[Experiment 6] Comparative Example 11 In Example 2, the photosensitive element (i) produced in Production Example 2 was replaced with the photosensitive element (i) produced in Production Example 3.
Example 1 except that i) was replaced and the substrate on which the red phosphor pattern precursor produced in Example 1 was formed was replaced by the substrate on which the blue phosphor pattern precursor produced in Comparative Example 8 was formed In the same manner as in 2, the green phosphor (G-5) was recovered.

Table 5 shows the results of evaluating the color difference of the obtained green phosphor (G-5). The untreated and unfired green phosphor was used as a reference for the color difference.

Comparative Example 12 In Example 3, the photosensitive element (ii) produced in Production Example 3 was replaced with the photosensitive element (i) produced in Production Example 4.
ii) and replacing the substrate on which the red and blue phosphor pattern precursors produced in Example 2 were formed with the substrate on which the blue and green phosphor pattern precursors produced in Comparative Example 11 were formed A red phosphor (R-5) was recovered in the same manner as in Example 3 except for the above.

Table 5 shows the evaluation results of the color difference of the obtained red phosphor (R-5). The untreated and unfired red phosphor was used as a reference for the color difference.

[0187]

[Table 5] From the results in Table 5, in the experimental operation 1 (Examples 1 to 3), the order of forming the phosphor pattern precursor on the substrate having the barrier ribs was determined in the order of red for the first color, blue for the second color, and blue for the third color. When the green phosphor pattern precursor is used, a change in the color difference of the phosphors recovered from the second color blue and third color green phosphor pattern precursors (the phosphor in the phosphor pattern precursor formed in red) Change in color difference due to the influence of the above). However, when the phosphor pattern precursor is formed on a substrate having barrier ribs in an order other than the experimental operation 1 (experimental operations 2 to 6), red,
The color difference of the red, green or blue phosphors recovered from the green and blue phosphor pattern precursor changed (0.0100 or more).

[0188]

According to the method for producing a phosphor pattern of the present invention, when a phosphor of the immediately preceding color is mixed in the collected phosphor when the phosphor is collected and reused, the chromaticity is not affected. The phosphor pattern can be manufactured with good yield, and the obtained phosphor pattern has no color difference change.

The CRT display, the field emission display, the fluorescent display, the radio emission display, and the back panel for a plasma display panel of the present invention are provided with a phosphor pattern which is excellent in light emission luminance and does not change in color difference.

[Brief description of the drawings]

FIG. 1 is a schematic view showing each step of a method for producing a phosphor pattern of the present invention.

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

FIG. 3 is a schematic view showing an example of a PDP substrate on which barrier ribs are formed.

FIG. 4 is a schematic view showing a state after the step (I) of the method for producing a phosphor pattern of the present invention is completed.

FIG. 5 is a schematic view showing a state after the step (I) of the method for producing a phosphor pattern of the present invention is completed.

FIG. 6 is a schematic diagram showing a state in which a pattern of a layer of a resin composition containing different phosphors is formed.

FIG. 7 is a schematic diagram showing a state in which a multicolor pattern composed of a photosensitive resin composition layer containing a phosphor is formed.

FIG. 8 is a schematic view showing an example of a back plate for a plasma display panel of the present invention.

FIG. 9 is a graph showing a change in chromaticity when other two color phosphors are mixed into each of a red phosphor, a blue phosphor, and a green phosphor.

[Description of Signs] 1 Substrate 2 Barrier rib 3 Lattice discharge space 4 Stripe discharge space 5 Photosensitive resin composition layer 5 ′ Photocured resin composition layer after photocuring 5′a First color pattern 5′b Second color 5'c Third color pattern 6 Embedded layer 8 Photomask 9 Active light 10 Phosphor pattern 10a First color phosphor pattern 10b Second color phosphor pattern 10c Third color phosphor pattern 11 Address electrode 12 Protective film 13 Dielectric layer 14 Display electrode 15 Front plate electrode

Continuation of the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/004 505 G03F 7/004 505 (72) Inventor Yoshiyuki Horibe 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Ibaraki Inside the research institute (72) Kazuya Sato 4-3-1-1, Higashicho, Hitachi, Ibaraki Prefecture Inside the Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd. (72) Mariko Shimamura 4-3-1-1, Higashicho, Hitachi, Ibaraki Hitachi, Ltd. (72) Inventor Seiji Tai, 4-3-1-1, Higashicho, Hitachi City, Ibaraki Pref., Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd.

Claims (3)

[Claims] 1. A method for producing a phosphor pattern in which a multicolor phosphor pattern is formed on a substrate by repeating photolithography on a photosensitive resin composition containing phosphors of different colors for each color. A method of manufacturing a phosphor pattern, comprising sequentially forming a phosphor pattern of red for a color, blue for a second color, and green for a third color. 2. A phosphor pattern produced by the method for producing a phosphor pattern according to claim 1. 3. A CRT display comprising the phosphor pattern according to claim 2 on a CRT substrate, a field emission display substrate, a fluorescent display panel substrate, a radio emission display substrate, or a plasma display panel substrate. , Field emission display, fluorescent display, radio emission display or back panel for plasma display panel.