JPH10186644A - Production of phosphor pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to form phosphor patterns of uniform shapes with high accuracy by forming positive type photosensitive resin layers on the substrate base and rib wall surfaces within the discharge spaces of a substrate for a plasma display panel formed with barrier ribs. SOLUTION: The positive photosensitive resin layers C5 are formed on the substrate base and rib wall surfaces within the discharge spaces of the substrate for the plasma display panel formed with the barrier ribs. The positive photosensitive resin layers C5 are irradiated imagewise with active rays and the irradiated parts thereof are removed by development. A negative photosensitive resin compsn. layer A7 contg. the phosphors and a thermoplastic resin layer B7 are thermally press bonded onto the substrate for the plasma display panel from which the positive type-photosensitive resin compsns. C5 are removed only in the desired parts by disposing the A layer 7 on the substrate side. These layers are irradiated imagewise with the active layers. The unnecessary parts of the theremally press bonded A layer 7 and B layer 6 are removed by development. The multicolor patterns consisting of the photosensitive resin compsns. contg. the phosphors developing red, green and blue are formed by repeating these stages. The unnecessary parts are removed by baking.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a method for manufacturing a phosphor pattern.

[0002]

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

In a PDP, a flat front plate and a rear plate made of glass are disposed in parallel and opposed to each other, and both are held at a fixed interval by barrier ribs provided therebetween. , And discharges in a space surrounded by the back plate and the barrier ribs.

[0004] In such a space, a phosphor for display is applied, and the phosphor is illuminated 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, there are:
A method of applying a slurry liquid or paste in which phosphors of each color are dispersed by a printing method such as screen printing has been proposed, and is disclosed in JP-A-1-115027, JP-A-1-124929, and JP-A-1-124930. And JP-A-2-155142.

However, since the above-mentioned phosphor dispersion slurry is in a liquid state, poor dispersion due to precipitation of the phosphor or the like is likely 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.

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-6-273925).
No.).

[0008] 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 heat-pressed (laminated) to the PDP. Embedded in the space of the substrate for use, then, using a negative film, imagewise exposed to actinic light such as ultraviolet light by a photographic method, then, with a developing solution such as an aqueous alkaline solution, to remove the unexposed portions, Unnecessary organic components are removed by firing, 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. Is also excellent. Furthermore, since a photographic method is used, a phosphor pattern can be formed with high accuracy.

However, when a photosensitive resin layer containing a luminous body is embedded in a space (in a cell) of the PDP substrate by lamination using a photosensitive element by a conventional method, the barrier rib wall surface and the space bottom surface are laid. It was difficult to form a phosphor pattern with a uniform thickness and shape.

Further, a method of embedding a phosphor-containing photosensitive resin layer in a space (in a cell) of the PDP substrate by lamination using a photosensitive element by a conventional method is repeated three times to obtain red, In the case of forming a pattern made of a photosensitive resin containing a phosphor that emits green and blue, a space where a pattern made of a photosensitive resin containing a phosphor is formed for the second time is partially partially formed of the first phosphor. Of the photosensitive resin layer containing the phosphor formed the second time is surrounded by the space embedded with the photosensitive resin containing There was a tendency to further deteriorate the uniformity.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide a PD
Excellent embedding into the space of the substrate for P (formation of the negative photosensitive resin composition layer containing the phosphor on the barrier rib wall surface and the bottom surface of the substrate for PDP), high accuracy, uniformity, and symmetry An object of the present invention is to provide a method of manufacturing a phosphor pattern capable of forming a phosphor pattern having an excellent shape.

Another object of the present invention is to provide a method for manufacturing a phosphor pattern which is more excellent in workability.

[0014]

According to the present invention, (I) a positive photosensitive resin layer (C) is formed on a bottom surface of a substrate and a wall surface of a rib in a discharge space of a substrate for a plasma display panel on which barrier ribs are formed. (II) a step of imagewise irradiating an actinic ray, (III) a step of removing an irradiated portion of the positive photosensitive resin layer (C) by development, and (IV) a positive photosensitive resin layer only at a desired portion. On the plasma display panel substrate from which (C) was removed, heating was performed with the negative photosensitive resin composition layer (A) containing the phosphor, the thermoplastic resin layer (B), and the (A) layer facing the substrate. Compression bonding step, (V) imagewise irradiation with actinic ray in the same pattern as step (II), (VI) phenomenon, and (A) layer and (B) heat-pressed in step (IV) due to phenomenon. Removing unnecessary portions of the layer,
(VII) repeating steps (II) to (VI),
Forming a multicolor pattern comprising a photosensitive resin composition containing a phosphor that emits red, green and blue light; and (VII)
I) A method of manufacturing a phosphor pattern, comprising a step of removing unnecessary components by firing.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION On a plasma display panel substrate from which a positive photosensitive resin layer (C) has been removed only at a desired portion in step (IV) of the present invention, a negative photosensitive resin containing a phosphor is provided. Resin composition layer (A) and thermoplastic resin layer (B)
In the step of heat-pressing with the (A) layer on the substrate side, for example, (1) (IV-1) a negative photosensitive resin layer (A) containing a phosphor on a plasma display panel substrate
And (2) (IV-2) a method of forming a thermoplastic resin layer (B) provided on a support film on a substrate for a plasma display panel on a substrate for a plasma display panel. It is carried out by a method of thermocompression bonding a photosensitive element formed of a multilayer film on which a negative photosensitive resin composition layer (A) containing a phosphor is provided.

As the substrate for a plasma display panel (substrate for PDP) on which barrier ribs are formed in the present invention, for example, a substrate in which electrodes and barrier ribs are formed on a substrate such as a glass plate or a synthetic resin plate can be mentioned. These substrates may be subjected to a surface treatment for transparent bonding.

The formation of the barrier rib is not particularly limited.
A known material can be used, and for example, a rib material containing silica, a thermosetting resin, a low-melting glass (such as lead oxide), a solvent, and 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 of 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. The barrier rib can be formed by a method such as a sand blast method or an embedding method.

The barrier ribs usually have a height of 20 to 500.
μm and a width of 20 to 200 μm. There is no particular limitation on the shape of the discharge space surrounded by the barrier ribs,
Although a stripe shape, a honeycomb shape, a triangular shape, an elliptical shape, and the like are possible, a grid-like or stripe-like discharge space is usually formed as shown in FIGS.

1 and 2, a barrier rib 2 is formed on a substrate 1. In FIG. 1, a grid-shaped discharge space 3 is formed, and in FIG. 2, 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. 1, 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.

The positive photosensitive resin layer (C) in the present invention is not particularly limited, but preferred examples thereof include a dissolution inhibitor-based positive resist and a chemically amplified positive resist. The dissolution inhibitor-based positive resist contains (h) a binder and (i) a photosensitizer.

(H) As the binder, a resin soluble in an aqueous alkali solution is used. For example, cresol novolak resin, phenol novolak resin, melamine-formaldehyde resin, polyethylene oxide, polyacrylamide, poly-p-vinylphenol, poly-p-vinylphenol Examples include methacrylic acid, polyacrylic acid, a copolymer of cresol and hydroxybenzyl alcohol, a copolymer of styrene and maleimide, polydimethylglutarimide, and poly-p-hydroxystyrene. (I) Photosensitizers include 1,2-naphthoquinonediazide compounds, 5-diazomeldrum acid, 2-diazo-1,3-diketocyclohexane-5-carboxylate, diphenyliodonium salts, triphenylsulfonium salts and the like. Is mentioned.

Examples of the chemically amplified positive resist include a photosensitive system in which a compound that generates an acid upon irradiation with an actinic ray and a compound that causes a reaction such as decomposition by the acid and solubilizes in a developing solution are used. , A combination of a compound generating an acid by light irradiation and an acetal compound, a combination of a polymer having an acetal or ketal group in the main chain, a combination of an enol ether compound, and a combination of a polymer having an orthoester group in the main chain , Tert-butyl ester of carboxylic acid or a polymer having tert-butyl carbonate group of phenol, and tert-butyl carboxylic acid in the molecule.
And a combination with a compound having an amyl ester structure.

Among these, a photosensitive system using a combination of a compound that generates an acid upon irradiation with actinic rays and a compound having a tert-amyl ester structure of a carboxylic acid in the molecule has high photosensitivity and high stability. It is more preferable because it is good and has a wide development latitude.

Among these, a photosensitive system using a combination of a compound that generates an acid upon irradiation with actinic rays and a compound having a tert-amyl ester structure of a carboxylic acid in the molecule is described in, for example, JP-A-59-45439.
Combinations of compounds as disclosed in Japanese Patent Publication No.

Among them, a nitrobenzyl derivative represented by the following general formula (A) or (A) (wherein, R represents an alkyl group having 1 to 16 carbon atoms, and is preferably a butyl group).

[0028]

Embedded image

[0029]

Embedded image And tert-amyl acrylate and a homopolymer of tert-amyl acrylate, or a copolymer with another copolymerizable monomer.

Examples of other copolymerizable monomers mentioned herein include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl acrylate, acrylonitrile, styrene, α-methylstyrene, diacetone acrylamide,
Vinyl toluene and the like can be mentioned, and these can be copolymerized by using one or more kinds in combination. The copolymerization amount of these other copolymerizable monomers is preferably 80 parts by weight or less based on 100 parts by weight of the total amount of all the monomers constituting the copolymer. More preferably, it is 70 to 20 parts by weight. 8
If it exceeds 0 parts by weight, the light sensitivity tends to decrease.

The copolymer is synthesized by a general solution polymerization method using the above-mentioned copolymerizable monomer in an organic solvent by using a polymerization initiator such as azobisisobutyronitrile, azobisdimethylvaleronitrile, and benzoyl peroxide. Can be obtained by As the organic solvent used at this time, methoxyethanol, ethoxyethanol, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanol, butyl acetate, chlorobenzene, dioxane, propylene glycol monomethyl ether and the like are used. This copolymer has a weight average molecular weight (in terms of polystyrene by GPC) of 5,000 to 300,000.
Preferably, 10,000 to 150,000
Is more preferable. This weight average molecular weight is
If it is less than 5,000, the mechanical strength of the resist tends to be weak, and if it exceeds 300,000, the developability (the property that the exposed portion can be easily removed by development) tends to be poor.

Examples of the developer for the positive photosensitive resin (C) include sodium metasilicate, sodium carbonate,
Aqueous solutions of inorganic alkalis such as sodium hydroxide, potassium carbonate and potassium hydroxide, and organic alkalis such as triethanolamine and tetramethylammonium hydroxide are included. The concentration of the aqueous alkali solution is 0.1 to 15% by weight.
Is preferable, and 0.5 to 5% by weight is more preferable. 0.1
If it is less than 15% by weight, the exposed portion may not be completely removed in a short time, and if it exceeds 15% by weight, the unexposed portion may be partially damaged. The developing method is performed by spraying the above-mentioned developer or immersing the developer in the developer.

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

(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 photosensitive resin composition containing the phosphor can be developed with various known developing solutions.
(A) The carboxyl group content (defined by the acid value (mgKOH / g)) of the film-imparting polymer 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 developing using an aqueous developing solution comprising water or an aqueous alkaline solution and one or more organic solvents, the acid value is preferably from 16 to 260. If the acid value is less than 16, development tends to be difficult,
If it exceeds 260, the developer resistance tends to decrease.

Furthermore, when an organic solvent developer such as 1,1,1-trichloroethane is used, it does not need to contain a carboxyl group.

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

For example, polyhydric alcohol acrylates or methacrylates (diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, tetrapropylene glycol diacrylate, tetrapropylene glycol diacrylate) Propylene glycol dimethacrylate, hexapropylene glycol diacrylate, hexapropylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triac Rate, pentaerythritol trimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate,
1,9-nonanediol diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, etc., epoxy acrylate or epoxy methacrylate (2,2-bis (4-methacryloxyethoxyphenyl) propane, 2,2-bis ( 4-acryloxyethoxyphenyl) propane, bisphenol A / epichlorohydrin epoxy resin, acrylic acid or methacrylic acid adduct, etc., and acrylate or methacrylate of phthalic anhydride / low molecular weight unsaturated polyester having a benzene ring in the molecule. Neopentyl glycol / acrylic acid = 1/2/2 (molar ratio), etc.), adduct of trimethylolpropane triglycidyl ether with acrylic acid or methacrylic acid, trimethylhexamethylene di Urethane acrylate compounds or urethane methacrylate compounds obtained by the reaction of a cyanic acid and a monohydric acrylic acid monoester or methacrylic acid monoester, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, polystyrylethyl Acrylate, polystyrylethyl methacrylate, 4- (2,
2,6,6-tetramethylpiperidinyl) acrylate, 4- (2,2,6,6-tetramethylpiperidinyl) methacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, and the like. These may be used alone or in combination of two or more. However, the photosensitive resin composition layer (A) containing the phosphor in the present invention needs to remove unnecessary organic components by baking, Polyethylene glycol dimethacrylate having good degradability is preferred.

(C) Examples of the photoinitiator which generates free radicals upon irradiation with actinic rays 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-1,2,2- Dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone-1,2,4- Diethylthioxanthone, 2-ethylanthraquinone, phenanthrenequinone, etc.), benzoin ether (benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, etc.), benzoin (methyl benzoin, ethyl benzoin, etc.), benzyl derivative (benzyl dimethyl ketal, etc.), 2 , 4,5 Triarylimidazole dimer, 2-(o-chlorophenyl) -4,5-diphenyl imidazole dimer, 2-(o-chlorophenyl) -
4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-phenylimidazole 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) The phosphor is not particularly limited.
A material mainly composed of a normal metal oxide is used.

As a red-colored phosphor, for example, Y _{2
O 2 S: Eu, Zn 3} (PO 4) 2: Mn, Y 3 0 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 a blue-emitting phosphor, 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.

The amount of component (a) is preferably from 10 to 90 parts by weight, more preferably from 20 to 80 parts by weight, based on 100 parts by weight of the total of components (a) and (b). preferable. When the compounding amount is less than 10 parts by weight, when the photosensitive element is supplied in a roll form,
When the phosphor-containing photosensitive resin composition exudes from the end of the roll (hereinafter, referred to as edge fusion), it becomes difficult to draw out the photosensitive element from the roll at the time of laminating the photosensitive element, and the extruded portion is a space of the PDP substrate. In some cases, there is a problem that the film is partially embedded excessively and the production yield is remarkably reduced, the film formability is lowered, and when the content exceeds 90 parts by weight, the sensitivity tends to be insufficient. .

The amount of the component (b) is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, based on 100 parts by weight of the total of the components (a) and (b). preferable. When the amount is less than 10 parts by weight, the sensitivity of the negative photosensitive resin composition containing the phosphor tends to be insufficient. Negative photosensitive resin composition containing the body or exuded from the edge by flow,
There is a tendency that film formability decreases.

The amount of the component (c) is 0.01 to 3 parts by weight based on 100 parts by weight of the total of the components (a) and (b).
It is preferably 0 parts by weight, more preferably 0.1 to 20 parts by weight. When the amount is less than 0.01 part by weight, the sensitivity of the negative photosensitive resin composition containing the phosphor tends to be insufficient. The absorption of actinic rays on the exposed surface of the photosensitive resin composition tends to increase, and the internal photocuring tends to be insufficient.

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

The photosensitive resin composition constituting the negative photosensitive resin composition layer (A) containing the phosphor in the present invention does not cause thickening for a long period of time and has good storage stability. And a compound having a carboxyl group. Examples of the compound having a carboxyl group include saturated fatty acids, unsaturated fatty acids, aliphatic dibasic acids, 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 these, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, citric acid and the like are preferred, and oxalic acid, malonic acid, citric acid and the like are more preferred, from the viewpoint of a high effect of suppressing thickening. These are used alone or in combination of two or more.

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

It is preferable to add a dispersant to the photosensitive resin composition constituting the photosensitive resin composition layer (A) containing the phosphor in the present invention in order to improve the dispersion of the phosphor. .

Examples of the dispersant include inorganic dispersants (silica gel type, bentonite type, kaolinite type, talc type, hectorite type, montmorillonite type, saponite type, beidellite type, etc.), and organic dispersants (aliphatic amide type, fat 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 per 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 it exceeds 100 parts by weight, the pattern formation accuracy (a pattern made of a negative photosensitive resin composition containing a phosphor,
After development, it is dimensionally accurate and has the desired shape.)
Tends to decrease.

In the present invention, the photosensitive resin composition constituting the photosensitive resin composition layer (A) containing the phosphor is bonded to the phosphor for preventing the phosphor from peeling off the PDP substrate after firing. It is preferable to use an adhesive.

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 negative photosensitive resin composition constituting the photosensitive resin composition layer (A) containing a phosphor according to the present invention includes a dye, a color former, a plasticizer, a pigment, a polymerization inhibitor,
A surface modifier, a stabilizer, an adhesion-imparting agent, a thermosetting agent, and the like can be added as needed.

The resin constituting the thermoplastic resin layer (B) in the present invention is not particularly limited as long as it is softened at the temperature during the heat and pressure bonding. For example, polyethylene, polypropylene, polyvinyl chloride, polyvinyl acetate , Polyvinylidene chloride, polystyrene, polyvinyl toluene, polyacrylate, polymethacrylate, copolymer of ethylene and vinyl acetate, copolymer of ethylene and acrylate, copolymer of vinyl chloride and vinyl acetate, styrene And acrylic acid or methacrylic acid ester, copolymer of vinyl toluene and acrylic or methacrylic acid ester, polyvinyl alcohol resin (polyacrylic acid ester or polymethacrylic acid ester hydrolyzate, poly Hydrolyzate of vinyl acetate, ethyl Hydrolyzate of a copolymer of ethylene and acrylate, hydrolyzate of a copolymer of ethylene and acrylate, hydrolyzate of a copolymer of vinyl chloride and vinyl acetate, styrene and acrylate or Hydrolysates of copolymers with methacrylic esters, hydrolysates of copolymers of vinyl toluene with acrylic esters or methacrylic esters, etc.), water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose esters, carboxy Examples thereof include water-soluble salts of alkyl starch, polyvinylpyrrolidone, and resins having a carboxyl group obtained by copolymerizing an unsaturated carboxylic acid and an unsaturated monomer copolymerizable therewith.

The thermoplastic resin layer (B) according to the present invention is preferably made of (e) from the viewpoint of preventing color mixing and improving workability.
Negative-type photosensitive resin composition comprising: a thermoplastic resin; (f) a photopolymerizable unsaturated compound having an ethylenically unsaturated group at a terminal; and (g) a photoinitiator that generates free radicals upon irradiation with actinic light. It can also be constituted by an object.

(E) As the thermoplastic resin, a negative photosensitive resin composition layer (A) containing a resin usable as a resin constituting the above-mentioned thermoplastic resin layer (B) and a phosphor is constituted. (A) usable for photosensitive resin composition
Film imparting polymers can be used.

(F) As the photopolymerizable unsaturated compound having an ethylenically unsaturated group at the terminal, the negative photosensitive resin constituting the negative photosensitive resin composition layer (A) containing the above-mentioned phosphor can be used. A (b) photopolymerizable unsaturated compound having an ethylenically unsaturated group at a terminal, which can be used in the composition, can be used.

(G) As the photoinitiator which generates free radicals upon irradiation with actinic rays, the negative photosensitive resin composition constituting the negative photosensitive resin composition layer (A) containing the above-mentioned phosphor is used. And (c) a photoinitiator that generates free radicals upon irradiation with actinic rays can be used.

The amount of component (e) is preferably from 10 to 90 parts by weight, more preferably from 20 to 80 parts by weight, based on 100 parts by weight of the total of components (e) and (f). preferable. When the compounding amount is less than 10 parts by weight, when the photosensitive element is used as a photosensitive element, the negative photosensitive resin composition tends to exude from an end portion due to flow, or the film-forming property tends to decrease, and 90 parts by weight. If the amount exceeds the above range, the sensitivity tends to be insufficient.

The amount of component (f) is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, based on 100 parts by weight of the total of components (e) and (f). preferable. If the amount is less than 10 parts by weight, the sensitivity tends to be insufficient. If the amount is more than 90 parts by weight, when the photosensitive element is used, the negative photosensitive resin composition is stained from the edge by the flow. And there is a tendency that the film formability is lowered.

The amount of the component (g) is 0.01 to 3 parts by weight based on 100 parts by weight of the total of the components (e) and (f).
It is preferably 0 parts by weight, more preferably 0.1 to 20 parts by weight. If the amount is less than 0.01 part by weight, the sensitivity tends to be insufficient. If the amount exceeds 30 parts by weight, the absorption of actinic rays on the exposed surface increases, resulting in insufficient light curing inside. It tends to be.

In the development step described below, the thermoplastic resin layer (B) is prepared by the method (1), wherein the negative photosensitive resin composition layer (A) containing the phosphor and the thermoplastic resin layer In the method (2), the positive photosensitive resin layer (C) and the negative photosensitive resin composition containing a phosphor may be used, wherein (B) can be developed using the same developer. It is preferable that the material layer (A) and the thermoplastic resin layer (B) can be developed using the same developer from the viewpoint of reducing the number of steps. Those which can be developed with the same developer include those which are soluble in water or an aqueous alkaline solution.

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

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

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

As the thermoplastic resin layer (B) soluble in an aqueous alkali solution, an unsaturated carboxylic acid and an unsaturated monomer copolymerizable therewith can be used so as to be developable by various known developers. The carboxyl group content of the resin having a carboxyl group obtained by copolymerization (acid value (m
gKOH / g) can be appropriately adjusted. For example, when developing using an aqueous alkali solution such as sodium carbonate or potassium carbonate, the acid value is 90 to 2
It is preferably 60. If the acid value is less than 90, development tends to be difficult, and if it exceeds 260,
The developer resistance tends to decrease. When developing using an aqueous developing solution comprising water or an aqueous alkaline solution and one or more organic solvents, the acid value is preferably from 16 to 260. When the acid value is less than 16, development tends to be difficult, and when it exceeds 260, developer resistance tends to decrease.

In order to improve the film properties of the thermoplastic resin layer (B), a plasticizer can be added to the resin constituting the thermoplastic resin layer (B).

As the plasticizer, polypropylene glycol, polyethylene glycol, dioctyl phthalate,
Examples include diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, biphenyl diphenyl phosphate, and the like.

In the method (1) of the present invention, the negative photosensitive resin composition layer (A) containing the phosphor is dissolved or mixed in a solvent capable of dissolving or dispersing the above-mentioned components. The thermoplastic resin layer (B) according to the present invention, which is used as a photosensitive element obtained by coating and drying a solution uniformly dispersed on a support film and thereby dissolving the resin constituting the solution, A known coating method such as a knife coating method, a roll coating method, a spray coating method, a gravure coating method, a bar coating method, a curtain coating method, etc. is formed on the support film by dissolving or mixing in a solvent to form a uniform solution. Can be formed into a film by coating and drying.

In the method (2) of the present invention, a thermoplastic resin layer (B) is provided on a support film, and a negative photosensitive resin composition layer (A) containing a phosphor is formed thereon. Used as a photosensitive element obtained by laminating.
As a lamination method, the components constituting the negative photosensitive resin composition are dissolved or mixed in a solvent capable of being dissolved or dispersed to form a uniformly dispersed solution, and the solution is formed on the thermoplastic resin layer (B). A method of coating and drying is used.

Examples of the solvent capable of dissolving or dispersing the components of the negative photosensitive resin composition layer (A) containing the phosphor include:
For example, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, γ-butyl lactone, N-methyl pyrrolidone,
Dimethylformamide, tetramethylsulfone, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, chloroform, methylene chloride,
Examples include methyl alcohol and ethyl alcohol.
These are used alone or in combination of two or more.

Examples of the solvent for dissolving the resin constituting the thermoplastic resin layer (B) include water and the above-mentioned solvents.

The support film is chemically and thermally stable and is composed of a flexible substance, for example, polyethylene terephthalate, polycarbonate, polyethylene, polypropylene and the like. Terephthalate and polyethylene are preferred, and polyethylene terephthalate is more preferred. The thickness of the support film is preferably 5 to 100 μm, more preferably 10 to 30 μm.

As a coating method, a known method can be used. For example, a knife coating method, a roll coating method,
Spray coating, gravure coating, bar coating,
Curtain coat method and the like can be mentioned.

The drying temperature is preferably from 60 to 130 ° C., and the drying time is preferably from 3 minutes to 1 hour.

The thickness of the negative photosensitive resin composition layer (A) containing a phosphor in the present invention is not particularly limited.
10 to 100 μm, preferably 20 to 80 μm
m is more preferable. If the thickness is less than 10 μm, the phosphor pattern after firing tends to be thin and the luminous efficiency tends to decrease. If the thickness exceeds 100 μm, the phosphor pattern after firing becomes thick and the emission area of the phosphor screen decreases. As a result, the luminous efficiency tends to decrease.

A releasable cover film can be further laminated on the negative photosensitive resin composition layer (A) containing the phosphor of the present invention.

As the cover film, polyethylene,
Examples include polypropylene, polyethylene terephthalate, and polycarbonate. The negative photosensitivity containing the cover film and the phosphor is less than the adhesive strength between the support film and the negative type photosensitive resin composition layer containing the phosphor (A). It is preferable that the adhesive strength with the resin composition layer (A) is smaller. The photosensitive element thus obtained can be stored in a roll.

The thickness of the thermoplastic resin layer (B) in the present invention is not particularly limited, and is preferably from 10 to 200 μm, and more preferably from 20 to 100 μm, from the viewpoint of embedding in the space of the PDP substrate. Is more preferable.

On the thermoplastic resin layer (B) in the present invention, a releasable cover film can be further laminated.

As the cover film, polyethylene,
Examples thereof include polypropylene, polyethylene terephthalate, and polycarbonate. The adhesive strength between the cover film and the thermoplastic resin layer (B) is smaller than the adhesive strength between the support film and the thermoplastic resin layer (B). Is preferred. The thermoplastic resin layer (B) thus formed on the film can be stored in a roll shape.

Hereinafter, each step of the method for producing a phosphor pattern of the present invention will be described in detail with reference to FIGS. FIGS. 3 and 4 are schematic views showing each step of the method for producing a phosphor pattern of the present invention. [(I) On the substrate bottom surface and the rib wall surface in the discharge space of the plasma display panel substrate on which the barrier rib is formed,
Step of Forming Positive Photosensitive Resin Layer (C)] A state in which the positive photosensitive resin layer (C) 5 is formed on the substrate bottom surface and the rib wall surface in the discharge space of the PDP substrate 1 on which the barrier ribs 2 are formed. Is shown in FIG. 3 (I).

In FIG. 3 (I), as a method for forming the positive photosensitive resin layer (C) 5 on the substrate bottom surface and the rib wall surface in the discharge space of the PDP substrate 1 on which the barrier rib 2 is formed, for example, And a method of applying a solution of the above-mentioned positive type photosensitive resin and drying the applied solution.

Further, a photosensitive element made of a positive photosensitive resin is prepared, and the positive photosensitive resin layer (C) is heated and pressed by the same step as the step (IV) described later, and then the thermoplastic resin is developed. By removing layer (B)
A positive photosensitive resin layer (C) 5 may be formed.

Further, a solution of a positive photosensitive resin is applied on the layer (B) of the film in which the thermoplastic resin layer (B) is provided on the support film and dried to include the positive photosensitive resin layer. A positive-type photosensitive resin layer (C) 5 may be formed by preparing a multilayer film and performing a process similar to the process (IV) described later.

The volume of the positive photosensitive resin layer (C) 5 formed in the discharge space is determined by the phosphor-containing photosensitive resin composition layer (A) at the time when the step (VI) described later is completed. It is preferable that the volume is 7 to 130% of the volume of the 7 ', more preferably 90 to 110%,
It is more preferable that they are the same, and it is most preferable that the shapes of the positive photosensitive resin layer (C) 5 and the photosensitive resin composition layer (A) 7 ′ containing the phosphor after photocuring match. If the formation amount of the positive photosensitive resin layer (C) is out of this range, the symmetry of the photosensitive resin composition layer (A) 7'b containing the phosphor of the second color in the step (VII) described later. Tends to decrease.

When a negative photosensitive resin is used for the thermoplastic resin layer (B), the positive photosensitive resin layer (C) 5
Is 70 to 130% of the total volume of the thermoplastic resin layer (B) after photocuring and the photosensitive resin composition layer (A) 7 'containing the phosphor after photocuring. It is preferable to set it as 90% to 110%,
It is more preferable that they are the same, and the positive photosensitive resin layer (C) 5 and the total of the photocured thermoplastic resin layer (B) and the phosphor-containing photosensitive resin composition layer (A) 7 ′ Most preferably, the shapes match.

By forming the positive photosensitive resin layer in this manner, in the step (IV) described later, irregularities around the discharge space where the photosensitive resin composition layer (A) containing the phosphor is formed are formed. When forming a multicolor pattern composed of a negative photosensitive resin composition layer containing a phosphor that emits red, green and blue in the step (VII) described below, The photosensitive resin composition layer (A) containing a phosphor that is uniform with high accuracy and excellent in symmetry can be formed. [(II) Step of irradiating actinic ray imagewise] actinic ray 1
FIG. 3 (II) shows a state where 0 is imagewise irradiated.

In FIG. 3 (II), as a method of imagewise irradiating the active light beam 10, the positive photosensitive resin layer (C) 5 is activated through the photomask 9 in the state of FIG. The light beam 10 can be illuminated imagewise.

As the actinic ray 10, a known actinic light source can be used, for example, a carbon arc, a mercury vapor arc,
Xenon arc, light generated from others, and the like.

Since the sensitivity of the positive photosensitive resin is usually maximum in the ultraviolet region, the active light source in that case should be one that effectively emits ultraviolet light. When the positive photosensitive resin is sensitive to visible light, visible light is used as the active light ray 10,
As the light source, a flood light bulb for photography, a sun lamp and the like can be used in addition to the above. [(III) Step of Removing Irradiated Portion by Development] FIG. 3 (III) shows a state in which the irradiated portion of active light is removed by development.
It was shown to. As the developing method in the present invention, for example,
When the above-mentioned chemically amplified positive resist is used for the positive photosensitive resin layer (C) after the state shown in FIG. 3 (II), it is usually heated at 60 to 150 ° C. for 1 to 30 minutes to expose the exposed portion. After completion of the solubilization reaction in a developing solution, a known developing solution such as an alkaline aqueous solution is used to perform development by a known method such as spraying, rocking immersion, brushing, and scrubbing to remove exposed portions. And the like. However, the developing solution used for developing the positive photosensitive resin layer (C) is developed by developing the positive photosensitive resin layer (C), thereby forming a negative photosensitive resin composition layer containing a phosphor described later. (A)
In addition, the photocured portion of the negative photosensitive thermosetting resin layer (B) must not be dissolved, peeled, or altered.

Examples of the base of the aqueous alkali solution include alkali hydroxide (such as hydroxide of lithium, sodium or potassium), alkali carbonate (such as carbonate or bicarbonate of lithium, sodium or potassium), and alkali metal phosphate (such as carbonate). Potassium phosphate, sodium phosphate, etc.), alkali metal pyrophosphate (sodium pyrophosphate, potassium pyrophosphate, etc.), alkali metal metasilicate (sodium metasilicate, potassium metasilicate, etc.), tetramethylammonium hydroxide, triethanol Examples include amines, and among them, sodium carbonate, tetramethylammonium hydroxide and the like are preferable.

The concentration of the aqueous alkali solution is preferably 0.1 to 15% by weight, more preferably 0.5 to 5% by weight.
If it is less than 0.1% by weight, the exposed portion may not be completely removed in a short time, and if it exceeds 15% by weight, the unexposed portion may be partially damaged.

Further, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like can be mixed in the alkaline aqueous solution. [(IV-1) Negative-type photosensitive resin composition layer containing phosphor on substrate for plasma display panel (A)
With the thermoplastic resin layer (B) placed on top of
(B) Step of thermocompression bonding of layer] and [(IV-2) Step of thermocompression bonding of photosensitive element (E) on plasma display panel substrate] On PDP substrate 1 on which barrier rib 2 is formed, FIG. 3 (IV) shows a state where the negative photosensitive resin composition layer (A) 7 containing the phosphor is laminated.
-1).

In FIG. 3 (IV-1), the barrier rib 2
As a method of laminating the negative photosensitive resin composition layer (A) 7 containing the phosphor on the PDP substrate 1 on which is formed, for example, a method of laminating using the photosensitive element and the like can be mentioned. Can be

In the case of using a photosensitive element, if a cover film is present on the photosensitive element, the cover film is removed, and a negative electrode containing a phosphor is formed on the surface of the PDP substrate on which the barrier ribs are formed. The photosensitive resin composition layer (A) 7 can be laminated by pressing with a pressure roll or the like so as to be in contact therewith.

The pressing pressure at this time is 50 to 1 × 1 in linear pressure.
It is preferable that the 0 ⁶ N / m. This pressure is 5
Is less than 0N / m, the negative photosensitive resin composition layer containing a phosphor (A) 7 is, there is a tendency that the embedding of the space on the substrate for PDP is lowered, the 1 × 10 ⁶ N / m If it exceeds, the barrier rib of the PDP substrate tends to be broken.

Further, from the viewpoint of further improving the embedding property of the negative photosensitive resin composition layer (A) 7 containing the phosphor into the space, the surface of the pressure roll is made to be flexible such as rubber and plastic. Rich materials can also be used. The thickness of the layer made of a material having a high flexibility is 200
It is preferable to set it to 400 μm.

Further, in order to further improve the embedding property of the negative photosensitive resin composition layer (A) 7 containing the phosphor into the space, the photosensitive element is heated while heating the photosensitive element with a heating roll 8 or the like. It can also be laminated by pressing against the surface of the substrate on which the barrier ribs are formed.

The heating temperature during thermocompression bonding is 10 to 130 ° C.
The temperature is preferably set to 20 to 120 ° C, more preferably 30 to 110 ° C. If the heating temperature is lower than 10 ° C., the negative photosensitive resin composition layer (A) 7 containing the phosphor tends to be unable to sufficiently adhere to the PDP substrate. Negative photosensitive resin composition layer containing (A)
7 tends to thermoset.

[0110] The pressing pressure during the heat pressing is 5 linear pressures.
It is preferably 0 to 1 × 10 ⁶ N / m. The crimping pressure is less than 50 N / m, the negative photosensitive resin composition layer containing a phosphor (A) 7 is, tend not to be sufficiently adhered to the PDP substrate, the 1 × 10 ⁶ N / m If exceeded,
The barrier ribs of the PDP substrate tend to be broken.

If the photosensitive element is heated as described above, it is not necessary to preheat the PDP substrate on which the barrier ribs have been formed, but the negative photosensitive resin composition layer (A) 7 containing a phosphor is required. In order to further improve the embedding property in the space, it is preferable to perform a pre-heat treatment on the PDP substrate.

Further, for the same purpose, the above-mentioned compression bonding and heating compression bonding can be performed under reduced pressure of 4 × 10 ³ Pa or less.

After the completion of the lamination as described above, 30
Heating can also be performed at a temperature in the range of ~ 150 ° C for 1 to 120 minutes. At this time, the support film can be removed as necessary.

A thermoplastic resin layer (B) 6 is disposed on the negative photosensitive resin composition layer (A) 7 containing a phosphor, and the negative photosensitive resin containing the phosphor is heated and pressed. FIG. 3 (IV-1) shows a state in which the composition layer (A) 7 and the thermoplastic resin layer (B) 6 are laminated.

In FIG. 3 (IV-1), a thermoplastic resin layer (B) 6 is disposed on a negative photosensitive resin composition layer (A) 7 containing a phosphor, and the thermocompression bonding is performed. For example, when a support film is present on the negative photosensitive resin composition layer (A) 7 containing the phosphor in the state of FIG. 3 (IV-1), the support film Is removed, the thermoplastic resin layer (B) 6 (if a cover film is present, the cover film is removed above the negative photosensitive resin composition layer (A) 7 containing the phosphor). After that, a method of thermocompression bonding with a heating roll 8 or the like is used.

The heating temperature during thermocompression bonding is 10 to 130 ° C.
The temperature is preferably set to 20 to 120 ° C, more preferably 30 to 110 ° C. If the heating temperature is lower than 10 ° C., the embedding property of the negative photosensitive resin composition layer (A) 7 containing the phosphor into the space of the PDP substrate tends to decrease. The negative photosensitive resin composition layer (A) 7 containing the body tends to be cured by heat.

Further, the pressing pressure at the time of heating and pressing is a linear pressure of 5
It is preferably 0 to 1 × 10 ⁶ N / m. If the pressure is less than 50 N / m, the embedding property of the negative photosensitive resin composition layer (A) 7 containing the phosphor into the space of the PDP substrate tends to decrease, and 1 × 10 ⁶ N / m If it exceeds m, the barrier rib of the PDP substrate tends to be broken.

If the thermoplastic resin layer (B) 6 is heated as described above, it is necessary to pre-heat the PDP substrate on which the negative photosensitive resin composition layer (A) 7 containing a phosphor is laminated. However, the negative photosensitive resin composition layer (A) containing a phosphor is more preferable because the negative photosensitive resin composition layer (A) 7 containing a phosphor is more improved in embedding into a space. It is preferable to pre-heat the PDP substrate on which No. 7 is laminated.

At this time, the preheating temperature is preferably 30 to 130 ° C., and the preheating time is preferably 0.5 to 20 minutes.

Further, from the viewpoint of further improving the embedding property of the negative photosensitive resin composition layer (A) 7 containing the phosphor in the space, the surface of the pressure roll is made to be flexible such as rubber and plastic. Rich materials can also be used.

The thickness of the layer made of a material having high flexibility is as follows.
The thickness is preferably 200 to 400 μm.

Further, for the same purpose, the above-mentioned press-bonding and heat-pressing operations can be performed under reduced pressure of 4 × 10 ³ Pa or less.

After the lamination is completed, the temperature is set at 30 to 150 ° C.
Can be heated for 1 to 120 minutes. At this time, if a support film exists on the thermoplastic resin (B) 6, the support film may be removed as necessary.

In the step (IV-1) of the present invention, two layers of the negative photosensitive resin composition layer (A) 7 containing a phosphor and the thermoplastic resin layer (B) 6 are simultaneously formed. It is also possible to laminate while heating and pressing. As the thermocompression bonding conditions when two layers are simultaneously thermocompression bonded, the conditions when thermocompression bonding of the thermoplastic resin layer (B) 6 can be used.

Next, a state in which the photosensitive element (E) is laminated on the PDP substrate 1 on which the barrier ribs 2 are formed is shown in FIG. 4 (IV-2).

In FIG. 4 (IV-2), the barrier rib 2
A method of laminating a photosensitive element (E) composed of a thermoplastic resin layer (B) 6 and a negative photosensitive resin composition layer (A) 7 containing the phosphor on the PDP substrate 1 on which is formed For example, when a cover film is present on the photosensitive element (E), after removing the cover film, a negative photosensitive resin composition containing a phosphor is formed on the surface of the PDP substrate on which the barrier ribs are formed. Material layer (A)
7 are arranged so as to be in contact with each other, and are heated and pressed by a heating roll 8 or the like.

The conditions of the thermocompression bonding, the preheating conditions of the PDP substrate, etc. are the same as in (IV-1).

In this manner, the negative photosensitive resin composition layer (A) 7 containing the phosphor can be uniformly formed on the substrate bottom surface and the rib wall surface in the discharge space of the PDP substrate. [(V) Step of irradiating actinic ray imagewise] actinic ray 10
FIG. 4 (V) shows a state in which is irradiated imagewise. In the step (V), a method of imagewise irradiating the actinic ray 10 is as follows. The photomask used in the step (II) is placed on the thermoplastic resin (B) 6 in the state of FIG. The actinic ray 10 can be imagewise irradiated through the photomask 9 having the same pattern. At this time, the thermoplastic resin layer (B)
In the case where a support film is present on 6, the actinic ray 10 may be irradiated imagewise while the support film is laminated, or the actinic ray 10 may be imaged after removing the support film. Irradiation may be performed.

At this time, the thermoplastic resin layer (B) 6
Is, when the negative photosensitive resin composition described above,
The photosensitive resin composition layer (A) 7 containing the phosphor and the thermoplastic resin layer (B) 6 are simultaneously photo-cured.

The thermoplastic resin layer (B) is prepared by using water, an alkali aqueous solution, an aqueous developer, an organic solvent or the like which does not dissolve the negative photosensitive resin composition layer (A) 7 containing the phosphor.
After removing 6 by dissolving, through photomask 9
The actinic ray 10 can be irradiated imagewise.

As the actinic ray 10, a known actinic light source can be used. For example, a carbon arc, a mercury vapor arc,
Xenon arc, light generated from others, 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 10 and the light source is as described above. In addition, a photo flood bulb, a sun lamp, and the like can be used. [(VI) Step of Removing Unwanted Parts of Layers (A) and (B) by Development] FIG. 4 (VI) shows a state where the unnecessary parts of layers (A) and (B) are removed by development. Was. In FIG. 4 (VI), reference numeral 7 'denotes a negative photosensitive resin composition layer containing a phosphor after photocuring.

In FIG. 4 (VI), as a developing method, for example, if a support film is present on the thermoplastic resin layer (B) 6 after the state of FIG. After removal, using a known developing solution such as an alkaline aqueous solution, an aqueous developing solution, an organic solvent, and the like, performing development by a known method such as spraying, rocking immersion, brushing, and scrubbing, and removing unnecessary portions. Can be However,
The developer used for developing the negative photosensitive resin composition layer (A) containing the phosphor is obtained by developing the negative photosensitive resin composition layer (A) containing the phosphor. The unexposed portion of the mold photosensitive resin layer (C) must not be dissolved, peeled off or altered.

In removing unnecessary portions, first, water that does not dissolve unexposed portions of the negative photosensitive resin composition layer (A) 7 containing the phosphor and the positive photosensitive resin layer (C) is used. After dissolving the thermoplastic resin layer (B) 6 by dissolving with an aqueous alkali solution, a semi-solvent aqueous solution, a semi-solvent alkaline aqueous solution, an organic solvent, or the like, using a developing solution, a negative photosensitive resin containing a phosphor is used. Unnecessary portions of the composition layer (A) 7 may be removed, and the thermoplastic resin layer (B) 6 may be used to develop the negative photosensitive resin composition layer (A) 7 containing the phosphor described above. When the developer can be developed using the same developer as the developer, the unnecessary portion of the negative photosensitive resin composition layer (A) 7 containing the phosphor and the thermoplastic resin can be used by using the developer. The layer (B) 6 can be removed in one step.

Unnecessary portions of the negative photosensitive resin composition layer (A) 7 containing the phosphor and the thermoplastic resin layer (B) 6
As a method for removing unnecessary portions of the above, the dry phenomenon can be used for each step alone or in one step.

At this time, when the negative photosensitive resin composition layer (A) 7 containing the phosphor is the negative photosensitive resin composition described above, the phosphor containing the photocured phosphor is contained. The photo-cured thermoplastic resin layer (B) will remain above the photosensitive resin composition layer 7 '.

Examples of the base of the aqueous alkali solution include alkali hydroxides (eg, hydroxides of lithium, sodium or potassium), alkali carbonates (eg, carbonates or bicarbonates of lithium, sodium or potassium), and alkali metal phosphates (eg, 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
The temperature is preferably adjusted in accordance with the developability of the negative photosensitive resin composition layer (A) 7 containing the phosphor and the thermoplastic resin layer (B) 6. Can be.

Further, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating the development, and the like 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 triacetone 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 monomethyl ether, diethylene glycol. Monobutyl ether and the like. 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.

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

Further, after the development, for the purpose of improving the adhesion and chemical resistance of the negative photosensitive resin composition layer 7 'containing the phosphor on the substrate bottom surface and the rib wall surface in the discharge space of the PDP substrate. Heating can also be performed. The temperature at this time is preferably 60 to 180 ° C.
The temperature is more preferably set to 180 ° C. However, even in this temperature range, if the positive photosensitive resin layer (C) is deformed or deteriorates, the positive photosensitive resin layer (C)
It is preferable to set the temperature within a range that does not cause deformation or deterioration. The heating time is 15 to 90
Minutes. [By repeating the steps of (VII) (II) to (VI),
Step of Forming Multicolor Pattern Consisting of Negative-Type Photosensitive Resin Composition Having Phosphor Emitting Red, Green and Blue] Each of the above steps (II) to (VI) is repeated to obtain red, green and blue. FIG. 5 shows a state in which a multicolor pattern composed of a negative photosensitive tree composition containing a color-forming phosphor is formed. In FIG. 5, 7'a is the first color pattern, 7'b
Is a second color pattern and 7'c is a third color pattern.

In the present invention, the photosensitive resin composition layer (A) 7 containing a single phosphor containing each of the phosphors that emit red, blue and green light is composed of any of the red, blue and green colors. It can be performed in any order.

After the steps (II) to (VI) are performed once to form the first color pattern, the second (III)
FIG. 5 (VII) shows a state where the steps up to the step have been completed. After the steps (II) to (VI) are performed twice to form the first and second color patterns, the third (II)
FIG. 5 (VII) shows a state where the process up to the step I) is completed.

In the present invention, the positive photosensitive resin layer (C) is provided in the discharge space other than the discharge space 4 'where the negative photosensitive resin composition layer containing the phosphor is to be formed in the step (IV). 5) or either of the negative-type photosensitive resin composition layer (A) 7 'containing a phosphor after photocuring is formed, and the symmetry around the discharge space when performing the step (IV). Is improved, so that the (A) layer having particularly excellent symmetry can be formed. [(VIII) Step of Removing Unwanted Parts by Firing] FIG. 5 (VIII) shows a state in which the step (VIII) in the present invention has been performed to form a multicolor phosphor pattern. FIG.
In (VIII), 11a is the first color phosphor pattern, 11b is the second color phosphor pattern, and 11c is the third color phosphor pattern.

In the step (VIII), 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 preferably from 350 to 800 ° C., and more preferably from 400 to 600 ° C. The firing time is preferably from 3 to 120 minutes, more preferably from 5 to 90 minutes.

[0153]

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

Production Example 1 [Preparation of Positive Photosensitive Resin Solution] Stirrer, reflux condenser,
240 g of propylene glycol monomethyl ether in a flask equipped with a thermometer, a dropping funnel and a nitrogen gas inlet tube
And heated to 90 ° C. in a nitrogen gas atmosphere. While maintaining the reaction temperature at 90 ± 2 ° C., a mixture of 120 g of tert-amyl acrylate, 80 g of methyl methacrylate and 2 g of azobisisobutyronitrile was dropped into the flask over 2 hours. Then, at 90 ° C ± 2 ° C, 3
After stirring for 1 hour, 1 g of azobisdimethyl valeronitrile was added to propylene glycol monomethyl ether 40 g.
The solution dissolved in g was dropped into the flask over 10 minutes, and then stirring was continued again at 90 ° C. ± 2 ° C. for 4 hours to obtain a tert-amyl acrylate copolymer solution having a weight average molecular weight of 39,000.

The thus obtained tert-amyl acrylate copolymer solution (240 g, polymer solid 100 g) was mixed with the following general formula (I)

[0156]

Embedded image 15 g of the p-nitrobenzyl derivative
A solution of a positive photosensitive resin was obtained.

Production Example 2 [Preparation of film-imparting polymer (a)] A flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer was charged with the components shown in Table 1 and placed under a nitrogen gas atmosphere. 80 ℃
And maintaining the reaction temperature at 80 ° C ± 2 ° C, Table 1
Was dropped uniformly over 4 hours. After dripping,
Stirring is continued at 80 ° C. ± 2 ° C. for 6 hours, and the weight average molecular weight is 8
A polymer (a) having a film property of 000 and an acid value of 130 mgKOH / g was obtained.

[0158]

[Table 1] Production Example 3 [Preparation of photosensitive element (A-R) including negative photosensitive resin composition layer containing red phosphor] Materials shown in Table 2 were mixed for 15 minutes using a raikai machine, and red A negative photosensitive resin composition solution containing the phosphor was prepared.

[0159]

[Table 2] The obtained solution is uniformly coated on a polyethylene terephthalate film having a thickness of 20 μm, dried with a hot air convection dryer at 80 to 110 ° C. for 10 minutes to remove the solvent, and a negative containing a red phosphor is removed. -Type photosensitive resin composition layer (A)
Was formed. The thickness of the negative photosensitive resin composition layer containing the obtained red phosphor after drying was 60 μm.

Next, a 25 μm-thick polyethylene film was laminated as a cover film on the negative-type photosensitive resin composition layer (A) containing the red phosphor to form a negative-type negative resin containing the red phosphor. A photosensitive element (A-R) containing the photosensitive resin composition layer (A) was produced.

Production Example 4 [Preparation of photosensitive element (AG) including negative photosensitive resin composition layer (A) containing green phosphor] Table 2
A negative photosensitive resin composition layer containing a green phosphor was formed in the same manner as in Production Example 3 except that the materials shown in Table 3 were used instead of the materials shown in Table 3. The thickness of the negative photosensitive resin composition layer containing the obtained green phosphor after drying was 60 μm.

[0162]

[Table 3] Next, in the same manner as in Production Example 3, a photosensitive element (AG) including a negative photosensitive resin composition layer (A) containing a green phosphor was produced.

Production Example 5 [Preparation of photosensitive element (AB) containing negative photosensitive resin composition layer (A) containing blue phosphor] Table 2
A negative type photosensitive resin composition layer containing a blue phosphor was formed in the same manner as in Production Example 3 except that the materials shown in Table 4 were used instead of the materials shown in Table 4. The thickness of the negative photosensitive resin composition layer containing the obtained green phosphor after drying was 60 μm.

[0164]

[Table 4] Next, in the same manner as in Production Example 3, a photosensitive element (AB) including a negative photosensitive resin composition layer (A) containing a green phosphor was produced.

Production Example 6 [Preparation of Film (B-1) Containing Thermoplastic Resin Layer (B)] A resin solution composed of the materials shown in Table 5 was uniformly applied on a polyethylene terephthalate film having a thickness of 20 μm. Then, a thermoplastic resin layer (B) was formed. The thickness of the obtained thermoplastic resin layer (B) after drying was 70 μm.

[0166]

[Table 5] Next, a polyethylene terephthalate film having a thickness of 25 μm was laminated as a cover film on the thermoplastic resin layer (B) to prepare a film (B-1) including the thermoplastic resin layer (B).

Production Example 7 [Preparation of photosensitive element (E-R) including thermoplastic resin layer (B) and negative-type photosensitive resin composition layer (A) containing red phosphor] Table 2 The materials were mixed using a raikai machine for 15 minutes to prepare a negative photosensitive resin composition solution containing a phosphor.

After the polyethylene terephthalate film of the film (B-1) containing the thermoplastic resin layer obtained in Production Example 6 was peeled off from the obtained solution, the thermoplastic resin layer (B) was removed.
And then dried with a hot air convection dryer at 80 to 110 ° C. for 10 minutes to remove the solvent, thereby forming a negative photosensitive resin composition layer (A) containing a red phosphor. . The thickness of the negative photosensitive resin composition layer containing the obtained red phosphor after drying was 60 μm.

Next, a 25 μm-thick polyethylene film was laminated as a cover film on the negative-type photosensitive resin composition layer (A) containing the red phosphor, and the negative-type negative resin containing the red phosphor was A photosensitive element (E-R) containing the photosensitive resin composition layer (A) was produced.

Production Example 8 [Preparation of photosensitive element (EG) containing thermoplastic resin layer (B) and negative photosensitive resin composition layer (A) containing green phosphor] Table 2 A negative photosensitive resin composition layer containing a green phosphor was formed in the same manner as in Production Example 7 except that the materials shown in Table 3 were used instead of the materials. The thickness of the negative photosensitive resin composition layer containing the obtained green phosphor after drying was 60 μm.

Then, a polyethylene film having a thickness of 25 μm is laminated as a cover film on the negative photosensitive resin composition layer (A) containing the green phosphor to form a negative photosensitive resin composition containing the green phosphor. A photosensitive element (EG) containing the photosensitive resin composition layer (A) was produced.

Production Example 9 [Preparation of photosensitive element (EB) including thermoplastic resin layer (B) and negative photosensitive resin composition layer (A) containing blue phosphor] Table 2 A negative photosensitive resin composition layer containing a blue phosphor was formed in the same manner as in Production Example 7 except that the materials shown in Table 4 were used instead of the materials. The thickness of the negative photosensitive resin composition layer containing the obtained blue phosphor after drying was 60 μm.

Next, a polyethylene film having a thickness of 25 μm is laminated as a cover film on the negative photosensitive resin composition layer (A) containing the blue phosphor, and the negative photosensitive resin composition layer containing the blue phosphor is adhered. A photosensitive element (EB) containing the photosensitive resin composition layer (A) was produced.

Next, the solution of the positive photosensitive resin was applied to the PDP substrate (striped barrier ribs, opening width between barrier ribs 150 μm, barrier rib width 70 μm, barrier rib height 150 μm) formed side. Coating and drying at 100 ° C. for 15 minutes were repeated five times, and the space was filled with a positive photosensitive resin.

Example 1 [Preparation of Fluorescent Pattern] [(I) Step of Forming Positive Photosensitive Resin Layer in Discharge Space of Plasma Display Panel Substrate Formed with Barrier Rib] PDP substrate (stripe-shaped barrier rib, Opening width between barrier ribs 150 μm, barrier rib width 70 μm
m, the barrier rib having a height of 150 μm) is coated with the solution of the positive photosensitive resin obtained in Production Example 1 by a roll coating method, and dried at 100 ° C. for 15 minutes to form a positive photosensitive resin. The conductive resin layer (C) was formed in the discharge space of the PDP substrate. [(II) Step of irradiating actinic rays imagewise] Then, a red photoresist mask is brought into close contact with the PDP substrate on which the positive photosensitive resin layer (C) is formed, and is manufactured by Oak Manufacturing Co., Ltd. Using an HMW-590 type exposure machine, 200m
Actinic rays were irradiated imagewise at J / cm ² . [(III) Step of Removing Irradiated Area of Positive-Type Photosensitive Resin Layer (C) by Development] Then, the mixture is heated at 120 ° C. for 15 minutes, and then treated with a 1% by weight aqueous solution of sodium metasilicate.
The exposed portion of the positive photosensitive resin layer (C) was removed by spray development for 0 second. Thereafter, the substrate was washed by spraying distilled water for 5 minutes, and dried by blowing hot air of 80 ° C. for 10 minutes. [(IV-1) Negative-type photosensitive resin composition layer containing phosphor on substrate for plasma display panel (A)
(B) Step of thermocompression bonding of layer (B) in a state where a thermoplastic resin layer is disposed on top of the above] Next, a negative photosensitive resin composition containing the phosphor obtained in Production Example 3 on this PBP substrate The photosensitive element (AR) containing the material layer (A) is peeled off from the polyethylene film using a vacuum laminator (VLM-1 type, manufactured by Hitachi Chemical Co., Ltd.).
Heat shoe temperature 30 ° C, laminating speed 1.5m
/ Min, the pressure is 4000 Pa or less, and the pressure is 2.
Lamination was performed at 5 × 10 ⁵ N / m.

Next, the photosensitive element (A-A) containing the negative photosensitive resin composition layer (A) containing the red phosphor was prepared.
R) peeling off the polyethylene terephthalate film,
The thermoplastic resin layer (B) obtained in Production Example 6 on the negative photosensitive resin composition layer (A) containing the red phosphor
While laminating the polyethylene terephthalate film from the film (B-1) containing, a laminator (trade name: HLM-3000 type, manufactured by Hitachi Chemical Co., Ltd.) was used, the laminating speed was 0.5 m / min, and the pressure was linear. 5.0 × by pressure
The layers were laminated at 10 ⁵ N / m. [(V) Step of irradiating actinic rays imagewise with the same pattern as the step (II)] Next, the thermoplastic resin layer (B)
The red photomask used in the step (II) is adhered to the polyethylene terephthalate film of the film (B-1) containing, and HMW-5 manufactured by Oak Manufacturing Co., Ltd.
Active light was imagewise irradiated at 100 mJ / cm ² using a 90 type exposure machine. [(VI) Step of Removing Unwanted Parts of Layers (A) and (B) Heat-Pressed in Step (IV-1) by Development]
Then, after irradiating with actinic light, leave at room temperature for 1 hour
70% at 30 ° C. using a 1% by weight aqueous sodium carbonate solution.
Spray developed for seconds. After the development, the film was washed by blowing distilled water for 5 minutes, and dried by blowing hot air of 80 ° C. for 10 minutes to obtain a pattern of a negative photosensitive resin composition layer (A) containing a red phosphor. . [By repeating the steps of (VII) (II) to (VI),
Step of Forming Multicolor Pattern Made of Negative-Type Photosensitive Resin Composition Having Phosphor Emitting Red, Green and Blue] Then, in the above-mentioned steps (II) to (VI), a photomask for red is used instead. Using a green photomask, a negative photosensitive element containing a red phosphor (A-
The steps (II) to (VI) are repeated using a negative photosensitive element (AG) containing a green phosphor in place of R) to obtain a negative photosensitive resin composition containing a green phosphor. The pattern of the material layer (A) was added.

Next, in the above steps (II) to (VI), a blue type photomask is used instead of the red type photomask, and the negative type photosensitive element (A-R) containing the red phosphor is used. Instead of using a negative photosensitive element (AB) containing a blue phosphor, (II)-
The process of (VI) is repeated, and the pattern of the negative photosensitive resin composition layer (A) containing the blue phosphor is added to the negative photosensitive resin composition containing the red, green and blue phosphors. A layer pattern was prepared. [(VIII) Step of Removing Unwanted Parts by Firing] Then, heat treatment (firing) was performed at 550 ° C. for 30 minutes to remove unnecessary resin components, and a phosphor pattern was formed in the space of the PDP substrate. . [Evaluation of Phosphor Pattern] A SEM photograph of a cross section of the obtained phosphor pattern was taken, the presence or absence of a gap between the phosphor layer and the bottom of the discharge space, the shape of the phosphor layer was observed, and the center of the bottom of the discharge space and The thickness of the phosphor layer at the center of the rib was measured, and the results are shown in Table 6.

[0178]

[Table 6] Example 2 A PDP substrate was manufactured in the same manner as in Example 1 except that the steps (IV-1) and (V-1) were changed to the following steps (IV-2) and (V-2). A phosphor pattern was formed in the space. Table 7 shows the evaluation of the phosphor pattern. [(IV-2) A photosensitive element (E) is provided on a substrate for a plasma display panel (a thermoplastic resin layer (B) is provided on a support film, and a negative photosensitive resin composition containing a phosphor is provided thereon). Multilayer film provided with material layer (A))
Step of thermocompression bonding] Next, a photosensitive composition comprising the thermoplastic resin layer (B) obtained in Production Example 7 and the negative photosensitive resin composition layer (A) containing a red phosphor on this PBP substrate. A vacuum laminator (manufactured by Hitachi Chemical Co., Ltd.,
The heat shoe temperature is 1
10 ° C., lamination speed 0.5 m / min, air pressure 400
Lamination was performed at 0 Pa or less and a pressure of 5.0 × 10 ⁵ N / m as a linear pressure. [(V-2) Step of irradiating actinic rays imagewise in the same pattern as the step (II)] Next, on the polyethylene terephthalate film of the photosensitive element, (II)
Adhere the red photomask used in the process of
Using an HMW-590 type exposure machine manufactured by Oak Works,
An actinic ray was imagewise irradiated at 00 mJ / cm ² .

[0179]

[Table 7] Comparative Example 1 A photosensitive element (A-R) including a negative-type photosensitive resin composition layer (A) containing a red phosphor was peeled off a polyethylene film on the same plasma display panel substrate as in Example 1. While using a laminator (manufactured by Hitachi Chemical Co., Ltd., trade name: HLM-3000 type), the laminating temperature was 110 ° C., and the laminating speed was 0.5 m /
The lamination was performed at a compression pressure of 5.0 × 10 ⁵ N / m in linear pressure.

Next, the photosensitive element (A-A) containing the negative photosensitive resin composition layer (A) containing the red phosphor was prepared.
R) A red photomask is adhered to the polyethylene terephthalate film of R), and H
Using an MW-590 type exposure machine, actinic rays were irradiated imagewise at 100 mJ / cm ² .

Next, after irradiating with actinic rays, the mixture was allowed to stand at room temperature for 1 hour, and then, using a 1% by weight aqueous sodium carbonate solution,
Spray development was performed at 30 ° C. for 70 seconds. After the development, the film was washed by blowing distilled water for 5 minutes, and dried by blowing hot air of 80 ° C. for 10 minutes to obtain a pattern of a negative photosensitive resin composition layer (A) containing a red phosphor. .

The same steps were repeated two more times to add a pattern for the negative photosensitive resin composition layer containing the green phosphor and a pattern for the negative photosensitive resin composition layer containing the blue phosphor. Thus, a pattern of a negative photosensitive resin composition layer containing red, green and blue phosphors was prepared.

Next, a heat treatment was performed under the same conditions as in the example to form a phosphor pattern in the space of the PDP substrate.

As a result of taking a SEM photograph of the cross section of the obtained phosphor pattern and observing the phosphor, a gap was formed between the phosphor layer and the bottom of the discharge space, and the phosphor layer reached the bottom of the discharge space. I didn't.

From these results, it is apparent that the conventional method of thermocompression-bonding a photosensitive element containing a negative photosensitive resin composition layer (A) containing a fluorescent substance has a positive photosensitive resin (C) and a thermoplastic resin layer. It can be seen that, compared to Examples 1 and 2, in which a film containing P was used, the formability of the phosphor pattern in the space of the PDP substrate (the embedding property on the barrier rib surface and the space bottom surface of the PDP substrate) was inferior. .

[0186]

As described above, the method for producing a phosphor pattern of the present invention comprises the steps of:
Excellent embedding into the space of the DP substrate (formability of the photosensitive resin composition layer containing the phosphor on the barrier rib wall surface and the bottom surface of the substrate in the discharge space of the PDP substrate) with a high precision and uniform shape A phosphor pattern can be formed.

Further, the present invention provides a method for producing a phosphor pattern which is more excellent in workability.

[Brief description of the drawings]

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

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

FIG. 3 is a schematic view showing each step of a method for manufacturing a phosphor pattern according to the present invention.

FIG. 4 is a schematic view showing each step of a method for manufacturing a phosphor pattern according to the present invention.

FIG. 5 is a schematic view showing a state in which a multicolor pattern composed of a photosensitive resin composition layer containing a phosphor is formed.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Substrate 2 Barrier rib 3 Lattice discharge space 4 Stripe discharge space 4 'Stripe discharge space forming negative photosensitive resin composition layer containing phosphor 5 Positive photosensitive resin layer (C) 6 Thermoplastic resin Layer (B) 7 Negative-type photosensitive resin composition layer containing phosphor (A) 7 ′ Negative-type photosensitive resin composition layer containing phosphor after photocuring (A) 7′a First-color fluorescence Body pattern 7'b Second-color phosphor pattern 7'c Third-color phosphor pattern 8 Heating roll 9 Photomask 10 Active ray 11a First-color phosphor pattern 11b Second-color phosphor pattern 11c Third-color phosphor pattern

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI H01J 9/227 H01J 9/227 E // C09D 4/06 C09D 4/06 (72) Inventor Yumiko Wada 4--13 Higashicho, Hitachi City, Ibaraki Prefecture 1 Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd. (72) Inventor Seiji Tai 4-13-1, Higashicho, Hitachi City, Ibaraki Pref., Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd.

Claims (6)

[Claims] (I) a step of forming a positive photosensitive resin layer (C) on a bottom surface and a rib wall surface in a discharge space of a plasma display panel substrate on which barrier ribs are formed,
(II) a step of irradiating actinic rays imagewise, (III) a step of removing an irradiated portion of the positive photosensitive resin layer (C) by development, and (IV) a positive photosensitive resin layer (C) only at a desired portion. ) On the substrate for a plasma display panel, from which the negative photosensitive resin composition layer (A) containing a phosphor and the thermoplastic resin layer (B) are heat-pressed with the (A) layer as the substrate side. (A) and (B) the layers (A) and (B) heat-pressed in the step (IV) due to the phenomenon (VI) due to the phenomenon (VI). Removing unnecessary parts of (VII), (II)
Steps (VI) to (VI) are repeated to form a multicolor pattern made of a photosensitive resin composition containing a phosphor that emits red, green and blue, and (VIII) a step of removing unnecessary components by firing. A method for producing a phosphor pattern. 2. The step (IV) is carried out on a plasma display panel substrate in a state where a thermoplastic resin layer (B) is disposed on a negative photosensitive resin layer (A) containing a phosphor. The method for producing a phosphor pattern according to claim 1, wherein the method is performed by thermocompression bonding the thermoplastic resin layer (B). 3. The removal of unnecessary portions of the negative photosensitive resin layer (A) and the thermoplastic resin layer (B) containing the phosphor in the step (VI) is performed by using the same developer. 3. The method for producing a phosphor pattern according to claim 2, wherein 4. A negative photosensitive resin composition layer containing a phosphor on a thermoplastic resin layer (B) provided on a support film on a substrate for a plasma display panel in the step (IV). The method for producing a phosphor pattern according to claim 1, wherein the method is performed by heat-pressing a photosensitive element comprising a multilayer film provided with (A). 5. The removal of the irradiated portion of the positive photosensitive resin layer (C) in the step (III), the negative photosensitive resin layer (A) containing the phosphor in the step (VI) and the thermoplastic resin 5. The method for producing a phosphor pattern according to claim 4, wherein the unnecessary portion of the layer (B) is removed by developing using the same developer. 6. A negative photosensitive resin composition layer (A) containing a phosphor, comprising: (a) a film property-imparting polymer; and (b)
The phosphor pattern according to claim 1, comprising a photopolymerizable unsaturated compound having an ethylenically unsaturated group at a terminal, (c) a photoinitiator that generates free radicals upon irradiation with actinic light, and (d) a phosphor. Manufacturing method.