JPH09265183A - Production of phosphor pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing phosphor patterns which improves the embedding property (moldability barrier rib wall surfaces of a substrate for PDP(plasma display panel) and photosensitive resin compsn. layer contg. the phosphors on a substrate surface) into the spaces of the substrate having ruggedness, such as substrate for the PDP, prevent color mixing and are capable of forming the phosphor patterns having a uniform shape with high accuracy only into the inside surfaces of recessed parts with allowance. SOLUTION: The photosensitive resin compsn. layer contg. the phosphors is formed on the substrate 1 having the ruggedness and a photosensitive thermoplastic resin layer is arranged on this compsn. layer and is thermally pressure bonded in this state thereto. The photosensitive element is irradiated imagewise with the active rays in the state that air contg. oxygen exists on the photosensitive resin layer and the unnecessary parts are removed by development. Further, the unnecessary parts are removed by baking.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD 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 the PDP, a flat plate-shaped front plate and a rear plate made of glass are arranged in parallel and opposite to each other, and both of them are held at a constant interval by a barrier rib provided therebetween. Also, the structure is such that discharge occurs in the space surrounded by the barrier ribs. In such a space, a phosphor for display is applied, and the phosphor is caused to emit light by ultraviolet rays generated from the sealing gas by discharge, so that the light can be visually recognized by an observer.

Conventionally, a method of providing this phosphor is as follows.
A method of applying a slurry solution or paste in which phosphors of each color are dispersed by a printing method such as screen printing has been proposed. And Japanese Patent Application Laid-Open No. 2-155142. However, since the above-mentioned phosphor dispersion slurry liquid is liquid, poor dispersion due to precipitation of the phosphor is likely to occur, and when a liquid photosensitive resist is used for the slurry liquid, it is preserved by promoting a dark reaction and the like. It has disadvantages such as poor stability. Furthermore, since printing methods such as screen printing are inferior in printing accuracy, there is a problem that it will be difficult to cope with future large screen PDPs.

In order to solve these problems, a method using a photosensitive element containing a phosphor (also referred to as a photosensitive film) has been proposed (Japanese Patent Laid-Open No. Hei 6-273925).
Issue). The method of using a photosensitive element means that a photosensitive resin layer containing a phosphor of a photosensitive element composed of a photosensitive resin layer containing a phosphor and a support film is heat-pressed (laminated) to form a PDP substrate. It is embedded in a space and then imagewise exposed to actinic light such as ultraviolet rays by a photographic method using a negative film. Then, the unexposed portion is removed with a developing solution such as an alkaline aqueous solution, and the unexposed portion is further baked. By removing the necessary organic components, the phosphor pattern is formed only on the necessary portions. Therefore, P
When forming a phosphor pattern in the space of the DP substrate,
It is not necessary to check the dispersibility of the phosphor, and the storage stability is superior to that of the phosphor dispersion slurry or paste. Furthermore, since a photographic method is used, a phosphor pattern can be formed with high accuracy.

However, when a photosensitive resin layer containing a phosphor is buried 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 left behind. It was difficult to form a phosphor pattern with a uniform thickness and shape.

[0006]

According to a first aspect of the present invention, the embedding property in a space of a substrate having irregularities such as a PDP substrate (a barrier rib wall surface of the PDP substrate and a photosensitive material containing a phosphor on the substrate surface). Of resinous resin composition layer)
The present invention provides a method for producing a phosphor pattern, which is excellent in color mixing, can prevent color mixture, and can form a highly accurate and uniform shape phosphor pattern with a margin only on the inner surface of the recess. In addition to the effect of the invention described in claim 1, the invention described in claim 2 provides a method for producing a phosphor pattern which is excellent in workability and suppression of film slippage. In addition to the effect of the invention described in claim 1 or 2, the invention described in claim 3 provides a method of manufacturing a phosphor pattern that is more excellent in workability. In addition to the effect of the invention described in claim 1, 2 or 3, the invention according to claim 4 provides a method for manufacturing a phosphor pattern having a better workability. The invention described in claim 5 provides a method for manufacturing a phosphor pattern having excellent workability, in addition to the effects of the invention described in claim 1, 2, 3 or 4.

[0007]

SUMMARY OF THE INVENTION The present invention comprises: (I) a substrate having irregularities, (A) a photosensitive resin composition layer containing (d) a phosphor, and (B) a photosensitive heat-sensitive layer. A step of thermocompression-bonding the layer (B) in a state where the plastic resin layer is arranged, (II) a step of imagewise irradiation with actinic rays in a state where a gas containing oxygen is present on the layer (B), The present invention relates to a method for producing a phosphor pattern, which comprises each step of (III) removing unnecessary portions by development and (IV) removing unnecessary portions by baking. The present invention also provides a method of forming a multicolor pattern comprising a photosensitive resin composition layer containing a phosphor that emits red, green, and blue by repeating the steps (I) to (III). The present invention relates to a method for producing the phosphor pattern for forming a multicolor phosphor pattern by performing the step (IV).

Further, in the present invention, (A) the photosensitive resin composition layer comprises (a) a film property imparting polymer, (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group at the terminal, (c)
The present invention relates to a method for producing the phosphor pattern, wherein free radicals are generated by irradiation with active light, and the generated free radicals include a photoinitiator that is easily deactivated by oxygen and (d) a phosphor. The present invention also provides (B) a photosensitive thermoplastic resin layer, (e) a thermoplastic resin, (f) a photopolymerizable unsaturated compound having an ethylenically unsaturated group at the end, and (g) irradiation with active light. To produce a free radical, and the produced free radical contains a photoinitiator that is easily deactivated by oxygen. Further, the present invention relates to the method for producing the phosphor pattern, wherein (A) layer and (B) layer are developed using the same developing solution in the step (III) of removing an unnecessary portion by development.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing a phosphor pattern of the present invention comprises: (I) a substrate having irregularities, (A) (d) a photosensitive resin composition layer containing a phosphor (B); ) In the state where the photosensitive thermoplastic resin layer is arranged, the step of heat-pressing the (B) layer; Irradiation step, (III)
The method is characterized by including each step of removing an unnecessary portion by development and (IV) removing an unnecessary portion by baking.

Examples of the substrate having irregularities in the present invention include a plasma display panel substrate (PDP substrate) having barrier ribs formed thereon. Examples of the PDP substrate include a substrate such as a glass plate or a synthetic resin plate on which electrodes and barrier ribs are formed, which may be subjected to a surface treatment for transparent bonding.
For forming the barrier rib, a known material can be used without any particular limitation. For example, a rib material containing silica, a thermosetting resin, a low-melting glass (such as lead oxide), a solvent, or the like can be used. In addition, in addition to the electrodes and barrier ribs, the PDP substrate may include a dielectric film, an insulating film, an auxiliary electrode,
A resistor or the like may be formed. There is no particular limitation on the method of forming these on a substrate.
An electrode can be formed on a substrate by a method such as vapor deposition, sputtering, plating, coating, or printing, and a barrier rib can be formed by a method such as a printing method, a sandblast method, or an embedding method.

In FIG. 1 and FIG. 2, P having a barrier rib is formed.
The schematic diagram of an example of the DP substrate is shown. The barrier ribs usually have a height of 20 to 500 μm and a width of 20 to 200 μm. The shape of the discharge space surrounded by the barrier ribs is not particularly limited, and may be a lattice shape, a stripe shape, a honeycomb shape, or 3 shapes.
Although it is possible to have a rectangular shape, an elliptical shape, or the like, a grid-shaped or stripe-shaped discharge space as shown in FIGS. 1 and 2 is usually formed. 1 and 2, a barrier rib 2 is formed on a substrate 1. In FIG. 1, a grid-like discharge space 3 is formed, and in FIG. 2, a stripe-like discharge space 4 is formed. The size of the discharge space is determined by the size and resolution of the PDP, and normally, in the case of the grid-like discharge space as shown in FIG. 1, the vertical and horizontal lengths are 50 μm to 1 mm.
If it is a striped discharge space such as
It becomes μm to 1 mm.

The photosensitive resin composition layer (A) in the present invention is not particularly limited as long as it is a layer containing (d) a photosensitive resin composition containing a phosphor as an essential component.
(A) a film-forming polymer, (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group at the end, (c) free radicals generated by irradiation with active light, and the generated free radicals are lost by oxygen. Live photoinitiator and (d)
A layer containing a phosphor and the like are mentioned as preferable ones.

The (a) film property imparting polymer in the present invention is preferably a vinyl copolymer, and the vinyl monomer used in the vinyl copolymer is, for example, acrylic acid, methacrylic acid, maleic acid or 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-butyl methacrylate, sec acrylate
-Butyl, 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, methacryl Octyl acrylate, nonyl acrylate, nonyl methacrylate, decyl acrylate, decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate , Eicosyl acrylate, eicosyl methacrylate, docosyl acrylate,
Docosyl methacrylate, cyclopentyl acrylate, cyclopentyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, cycloheptyl acrylate, cycloheptyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, methoxyethyl acrylate , Methoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, 2-hydroxyethyl acrylate , 2-hydroxyethyl methacrylate, dimethylamino acrylate Chill, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, 2-chloroethyl acrylate, 2-chloroethyl methacrylate, 2-fluoroethyl acrylate, methacryl Acid 2-
Fluoroethyl, 2-cyanoethyl acrylate, 2-cyanoethyl methacrylate, styrene, α-methylstyrene, vinyltoluene, vinyl chloride, vinyl acetate, N-vinylpyrrolidone, butadiene, isoprene, chloroprene, acrylamide, methacrylamide, acrylonitrile, methacryl Lonitrile and the like. These are used alone or in combination of two or more.

The weight average molecular weight of the film-forming polymer (a) in the present invention is preferably 5,000 to 300,000, more preferably 20,000 to 150,000. This weight average molecular weight is 5,
When it is less than 000, the film-forming property and flexibility of the photosensitive element tend to decrease,
If it exceeds 000, the developability (the property that the unnecessary portion can be easily removed by the development) tends to be deteriorated. The weight average molecular weight is a value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve.

Further, the carboxyl group content (acid value (mgKO
H / g)) can be adjusted appropriately. For example, when developing using an alkaline aqueous solution such as sodium carbonate or potassium carbonate, the acid value is 90 to 260.
It is preferable that If the acid value is less than 90, development tends to be difficult, and if it exceeds 260, the developer resistance (the property that a portion which is not removed by development and remains as a pattern and is not attacked by the developer) decreases. Tend to. In the case of developing using an aqueous developer containing water or an alkaline aqueous solution and one or more organic solvents, the acid value is preferably 16 to 260. If the acid value is less than 16, development tends to be difficult, and
If it exceeds 0, the developer resistance tends to decrease. Further, when an organic solvent developer such as 1,1,1-trichloroethane is used, it does not need to contain a carboxyl group.

The photopolymerizable unsaturated compound having an ethylenically unsaturated group at the terminal (b) in the present invention has conventionally been
All those known as photopolymerizable polyfunctional monomers can be used. For example, the following general formula (I)

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

Embedded image (Wherein R ¹ represents a hydrogen atom, a methyl group, an ethyl group, a propyl group or a trifluoromethyl group, and m and n each independently represent an integer of 1 to 20) and the like. Is mentioned.

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

Specifically, examples of the monomer having one unsaturated bond include ester monomers of acrylic acid or methacrylic acid (methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acryl). Acid n-propyl, n-propyl methacrylate, iso-propyl acrylate, iso-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, acrylic acid
sec-butyl, sec-butyl methacrylate, te acrylate
rt-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, acrylic acid Dodecyl, dodecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, eicosyl acrylate, eicosyl methacrylate, docosyl acrylate, docosyl methacrylate, cyclopentyl acrylate, Cyclopentyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, cycloheptyl acrylate, methacryl Cycloheptyl acid, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate, methacrylic acid Dimethylaminopropyl, 2-chloroethyl acrylate, 2-chloroethyl methacrylate, 2-fluoroethyl acrylate, 2-fluoroethyl methacrylate, acrylic acid 2
-Cyanoethyl, 2-cyanoethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, etc.), styrene Monomer (styrene, α-methylstyrene, pt-butylstyrene, etc.), polyolefin monomer (butadiene, isoprene, chloroprene, etc.), vinyl monomer (vinyl chloride, vinyl acetate, etc.), nitrile monomer (acrylonitrile, methacrylic Lonitrile, etc.), 1- (methacryloyloxyethoxycarbonyl)
-2- (3'-chloro-2'-hydroxypropoxycarbonyl) benzene and the like.

Examples of the monomer having two unsaturated bonds include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate. Ethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, hexapropylene glycol dimethacrylate, hexapropylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, butylene glycol diacrylate, butylene glycol Jime Acrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,3-butanediol diacrylate,
1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,5-pentanediol diacrylate, 1,5-pentanediol dimethacrylate,
1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, bisphenol A
Diacrylate, bisphenol A dimethacrylate,
2,2-bis (4-acryloxyethoxyphenyl) propane, 2,2-bis (4-methacryloxyethoxyphenyl) propane, 2,2-bis (4-acryloxydiethoxyphenyl) propane, 2,2- Bis (4-methacryloxydiethoxyphenyl) propane, 2,2-bis (4-acryloxypolyethoxyphenyl) propane 2,2-bis (4-methacryloxypolyethoxyphenyl) propane (formula of the general formula (I) Medium, Y

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

Examples of the monomer having three unsaturated bonds include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, ethylene oxide-modified trimethylolpropane triacrylate, and ethylene oxide. Modified trimethylolpropane trimethacrylate, trimethylolpropane triglycidyl ether triacrylate, trimethylolpropane triglycidyl ether trimethacrylate and the like can be mentioned. Examples of the monomer having four unsaturated bonds include tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol tetraacrylate, and pentaerythritol tetramethacrylate.

Examples of the monomer having five unsaturated bonds include dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate and the like. Examples of the monomer having six unsaturated bonds include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. Any of these unsaturated bond-containing monomers may be those capable of radical polymerization by light irradiation, and these unsaturated bond-containing monomers may be used alone or in combination of two or more. Used in combination.
In addition, the (A) photosensitive resin composition layer in the present invention needs to be removed of unnecessary components by baking during the production of the phosphor pattern, and thus the (b) light having an ethylenically unsaturated group at the terminal is used. Among the polymerizable unsaturated compounds, polyethylene glycol dimethacrylate, which has good thermal decomposability, is more preferable.

Examples of the photoinitiator (c) in the present invention, which produces free radicals upon irradiation with active light, and in which the produced free radicals are easily deactivated by oxygen, include aromatic ketones (benzophenone, N, N '). -Tetramethyl-
4,4'-diaminobenzophenone (Michler's ketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,4 -Diethylthioxanthone, 2-
Ethylanthraquinone, phenanthrenequinone, etc.), benzoin ether (benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, etc.), benzoin (methylbenzoin, ethylbenzoin, etc.), 2,4,5-triarylimidazole dimer (2- (O-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,
5-di (m-methoxyphenyl) imidazole dimer,
2- (o-fluorophenyl) -4,5-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- ( 2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer),
Acridine derivative (9-phenylacridine, 1,7-
Bis (9,9′-acridinyl) heptane, etc.) and the like. These can be removed by development when the photocurability of the exposed portion of the (A) photosensitive resin composition formed on a portion other than the inner surface of the recess is insufficient in the method for producing a phosphor pattern described later. Thus, they are used alone or in combination of two or more. 3 is a schematic view showing the inner surface of the recess to which the (A) photosensitive resin composition layer of the present invention is adhered. In FIG. 3, the inner surface 5 of the recess is shown.
Is shown as a shaded area.

Further, in the method for producing a phosphor pattern of the present invention, the photocurability of the exposed portion of the photosensitive resin composition (A) formed on a portion other than the inner surface of the recess becomes insufficient, so that the portion is developed. For example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1-
(4- (Methylthio) phenyl) -2-morpholinopropanone-1,2,2-dimethoxy-1,2-diphenylethan-1-one, benzyldimethylketal and the like are used alone as the component (c) in the present invention. Although it is not preferable to use the above, it can be used to the extent that the above effects are not impaired.

The phosphor (d) in the present invention is not particularly limited, and a phosphor mainly composed of a normal metal oxide can be used. Examples of the phosphor that emits red light include Y ₂ O ₂
S: Eu, Zn ₃ (PO ₄ ) ₂ : Mn, Y ₂ O ₃ : Eu, YV
O ₄ : Eu, (Y, Gd) BO ₃ : Eu, γ-Zn ₃ (PO ₄ )
₂ : Mn, (ZnCd) S: Ag + In ₂ O and the like. Examples of green-colored phosphors include ZnS: C
u, Zn ₂ SiO ₄ : Mn, ZnS: Cu + Zn ₂ Si
O ₄ : Mn, Gd ₂ O ₂ S: Tb, Y ₃ Al ₅ O ₁₂ : Ce,
ZnS: Cu, Al, Y ₂ O ₂ S: Tb, ZnO: Zn,
ZnS: Cu, Al + In ₂ O ₃ , LaPO ₄ : Ce, T
_{b, BaO · 6Al 2 O 3} : Mn , and the like. Examples of the blue-emitting phosphor include ZnS: Ag and ZnS:
Ag, Al, ZnS: Ag, Ga, Al, ZnS: A
g, Cu, Ga, Cl, ZnS: Ag + In ₂ O ₃ , Ca
₂ B ₅ O ₉ Cl: Eu ²⁺ , (Sr, Ca, Ba, Mg) ₁₀ (P
O ₄ ) ₆ Cl ₂ : Eu ²⁺ , Sr ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu ²⁺ ,
BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , BaMgAl ₁₄ O ₂₃ : E
u ²⁺ , BaMgAl ₁₆ O ₂₆ : Eu ^{2+ and the} like.

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

The blending amount of the component (a) in the present invention is
The total amount of the component (a) and the component (b) is preferably 10 to 90 parts by weight based on 100 parts by weight, and more preferably 20 to 8 parts by weight.
More preferably, it is 0 parts by weight. If this blending amount is 1
If it is less than 0 part by weight, when it is supplied in a roll form as a photosensitive element, the phosphor-containing photosensitive resin exudes from the end portion of the roll (hereinafter referred to as edge fusion), so that the photosensitive element is fed out from the roll during lamination. 90 parts by weight tend to occur, and the exuded part is partially excessively embedded in the space of the PDP substrate, resulting in problems such as a significant decrease in manufacturing yield and a decrease in film formability. If it exceeds, the sensitivity tends to be insufficient.

The blending amount of the component (b) in the present invention is
The total amount of the component (a) and the component (b) is preferably 10 to 90 parts by weight based on 100 parts by weight, and more preferably 20 to 8 parts by weight.
More preferably, it is 0 parts by weight. If this blending amount is 1
If it is less than 0 parts by weight, the sensitivity of the photosensitive resin composition containing the phosphor tends to be insufficient, and if it exceeds 90 parts by weight, when it is used as a photosensitive element, the photosensitive resin containing the phosphor is used. The composition tends to exude from the edges due to the flow, and the film-forming property tends to deteriorate.

The blending amount of the component (c) in the present invention is
The amount is preferably 0.01 to 30 parts by weight based on 100 parts by weight of the total of the components (a) and (b).
More preferably, it is 1 to 20 parts by weight. If the content is less than 0.01 parts by weight, the sensitivity of the photosensitive resin composition containing the phosphor tends to be insufficient, and if it exceeds 30 parts by weight, the photosensitive resin composition containing the phosphor is present. The absorption of active light on the exposed surface of the product tends to increase, and internal photocuring tends to be insufficient. Further, the component (c) is blended so that the photocurability of the exposed portion of the (A) photosensitive resin composition formed on a portion other than the inner surface of the recess becomes insufficient, so that the portion can be removed by the development described later. The amount can be adjusted appropriately.

The blending amount of the component (d) in the present invention is
The amount is preferably from 10 to 300 parts by weight, more preferably from 50 to 250 parts by weight, based on 100 parts by weight of the total of the components (a), (b) and (c).
It is particularly preferable that the amount is 0 to 200 parts by weight. If the content is less than 10 parts by weight, the luminous efficiency tends to decrease when light is emitted as a PDP, and if it exceeds 300 parts by weight, the film-forming property decreases when used as a photosensitive element, Flexibility tends to decrease.

The photosensitive resin composition constituting the photosensitive resin composition layer (A) in the present invention contains a compound having a carboxyl group in order to prevent the viscosity from increasing for a long period of time and to improve the storage stability. Can be included. 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 them, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, citric acid and the like are preferable, and oxalic acid, malonic acid, citric acid and the like are more preferable in terms of a high effect of suppressing thickening. These are used alone or in combination of two or more.

The compounding amount of the compound having a carboxyl group is 0.01 to 30 with respect to 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.

A dispersant is preferably added to the photosensitive resin composition constituting the photosensitive resin composition layer (A) in the present invention in order to improve the dispersion of the phosphor. As the dispersant, an inorganic dispersant (silica gel type, bentonite type, kaolinite type, talc type, hectorite type, montmorillonite type, saponite type, beidellite type, etc.),
Organic dispersant (aliphatic amide type, aliphatic ester type, polyethylene oxide type, sulfuric acid ester type anion activator, polycarboxylic acid amine salt type, polycarboxylic acid type, polyamide type, high molecular weight polyether type, acrylic copolymer system,
Special silicon type etc.) and the like. These can be used alone or in combination of two or more.

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

A binder is used in the photosensitive resin composition constituting the photosensitive resin composition layer (A) in the present invention in order to prevent the phosphor from peeling off from the PDP substrate after firing. It is preferable. Examples of the binder include a low-melting glass, a metal alkoxide, and a silane coupling agent. These are used alone or in combination of two or more. The amount of the binder used is not particularly limited, and is 0.01% with respect to 100 parts by weight of the component (d).
To 100 parts by weight, preferably 0.05 to 50
More preferably, the amount is 0.1 to 30 parts by weight. If the amount is less than 0.01 part by weight, the binding effect of the phosphor tends not to be exhibited, and if it exceeds 100 parts by weight, the luminous efficiency tends to decrease.

The photosensitive resin composition constituting the photosensitive resin composition layer (A) in the present invention includes a dye, a color former, a plasticizer, a pigment, a polymerization inhibitor, a surface modifier, a stabilizer,
An adhesion promoter, a thermosetting agent, etc. can be added as needed.

The viscosity of the photosensitive resin composition layer (A) in the present invention at 100 ° C. is preferably 1 to 1 × 10 ⁷ Pa · sec, and more preferably 2 to 1 × 10 ⁶ Pa · sec. Is more preferable, 5 to 1 × 10 ⁵ Pa · sec is particularly preferable, and 10 to 1 × 10 ⁴ Pa · sec is extremely preferable. If the viscosity at 100 ° C. is less than 1 Pa · sec, the viscosity at room temperature becomes too low and the photosensitive resin composition layer (A) tends to exude from the end due to flow when used as a photosensitive element. Yes, the film-forming property tends to decrease. On the other hand, when it exceeds 1 × 10 ⁷ Pa · sec, the formability of the (A) photosensitive resin composition layer on the inner surface of the concave portion of the substrate having irregularities to be described later tends to decrease.

The (A) photosensitive resin composition layer in the present invention is made into a uniformly dispersed solution by dissolving or mixing each of the components constituting the photosensitive resin composition layer in a solvent capable of dissolving or dispersing the support film. It can be obtained as a photosensitive element by applying and drying it.

Examples of the solvent capable of dissolving or dispersing the above components include toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, γ-butyrolactone, N-methylpyrrolidone, dimethylformamide, tetramethylsulfone, Examples include diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, chloroform, methylene chloride, methyl alcohol, ethyl alcohol and the like. These are used alone or in combination of two or more.

The support film includes, for example, polyethylene terephthalate, polycarbonate, polyethylene, polypropylene which are chemically and thermally stable and are made of a flexible material, and among them, polyethylene is preferable. Terephthalate and polyethylene are preferable, and polyethylene terephthalate is more preferable. Since the support film must be removable from the photosensitive resin composition layer (A) later, it may be surface-treated or made of a material that makes the removal impossible. Don't The thickness of the support film is 5
The thickness is preferably -100 μm, more preferably 10-30 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 60-
The temperature is preferably 130 ° C., and the drying time is 3 minutes to 1
It is preferable to set the time.

The thickness of the photosensitive resin composition layer (A) in the present invention is not particularly limited, but is preferably 10 to 200 μm, more preferably 20 to 120 μm, and 30 to 80 μm. Is particularly preferred. If this thickness is less than 10 μm, the phosphor pattern after firing tends to be thin, and the luminous efficiency tends to decrease.
If it exceeds m, the phosphor pattern after firing becomes thick, and the light emitting area of the phosphor screen tends to be reduced, so that the light emitting efficiency tends to decrease.

A peelable cover film can be further laminated on the (A) photosensitive resin composition layer in the present invention. Examples of the cover film include polyethylene, polypropylene, polyethylene terephthalate, and polycarbonate. The support film and (A)
The adhesive force between the cover film and the (A) photosensitive resin composition layer is preferably smaller than the adhesive force with the photosensitive resin composition layer. The photosensitive element thus obtained can be stored in a roll.

The (B) photosensitive thermoplastic resin layer in the present invention is not particularly limited as long as it is photosensitive and softens at the temperature during thermocompression bonding. For example, (e) thermoplastic resin, (F) a photopolymerizable unsaturated compound having an ethylenically unsaturated group, and (g) a photoinitiator that produces free radicals upon irradiation with active light, and the produced free radicals are easily deactivated by oxygen. Photosensitive resin compositions and the like are preferable as those from the viewpoint of preventing color mixture and improving workability.

Examples of the thermoplastic resin (e) in the present invention include polyethylene, polypropylene, polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride, polystyrene, polyvinyltoluene, polyacrylic acid ester, polymethacrylic acid ester and ethylene. Copolymer of vinyl acetate, copolymer of ethylene and acrylic acid ester, copolymer of vinyl chloride and vinyl acetate, copolymer of styrene and acrylic acid ester or methacrylic acid ester, vinyl toluene and acrylic acid ester or methacrylic acid Copolymer with acid ester, polyvinyl alcohol resin (hydrolyzate of polyacrylic acid ester or polymethacrylic acid ester, hydrolyzate of polyvinyl acetate, hydrolyzate of copolymer of ethylene and vinyl acetate, ethylene And acrylic ester Hydrolyzate of copolymer, hydrolyzate of copolymer of vinyl chloride and vinyl acetate, hydrolyzate of copolymer of styrene and acrylic acid ester or methacrylic acid ester, vinyltoluene and acrylic acid ester or Hydrolyzate of copolymer with methacrylic acid ester), water-soluble salt of carboxyalkyl cellulose,
Water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polyvinylpyrrolidone, resins having a carboxyl group obtained by copolymerizing an unsaturated carboxylic acid and an unsaturated monomer copolymerizable therewith, and the like. . Further, the (a) film property imparting polymer which can be used in the photosensitive resin composition constituting the above-mentioned (A) photosensitive resin composition layer can be used. These are used alone or in combination of two or more.

The photopolymerizable unsaturated compound having an ethylenically unsaturated group at the terminal (f) can be used in the photosensitive resin composition constituting the above-mentioned photosensitive resin composition layer (A) (b). A photopolymerizable unsaturated compound having an ethylenically unsaturated group at the terminal can be used.

(G) As the photoinitiator which produces free radicals upon irradiation with actinic light, and the produced free radicals are easily deactivated by oxygen, the photosensitizer constituting the above-mentioned (A) photosensitive resin composition layer is used. (C) that can be used in a resin composition
Examples include photoinitiators that generate free radicals upon irradiation with active light, and the generated free radicals are easily deactivated by oxygen. These are (B) a photosensitive thermoplastic resin layer formed on a portion other than the inner surface of the recess. Since the photocurability of the exposed part becomes insufficient, it can be used so that the part can be removed by development.

The amount of component (e) to be added is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, with the total amount of components (e) and (f) being 100 parts by weight. preferable. If the blending amount is less than 10 parts by weight, when it is used as a photosensitive element, the photosensitive resin composition tends to exude from the end portion due to flow, the film formability may be deteriorated, and 90 parts by weight may be used. If it exceeds, the sensitivity tends to be insufficient.

The compounding amount of the component (f) is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, when the total amount of the components (e) and (f) is 100 parts by weight. 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, it exudes from the edge due to the flow and the film-forming property is deteriorated. Tend to do so.

The blending amount of the component (g) is 0.01 to 3 relative to 100 parts by weight of the total amount of the components (e) and (f).
The amount is preferably 0 part by weight, more preferably 0.1 to 20 parts by weight. If the amount is less than 0.01 parts by weight, the sensitivity tends to be insufficient, and if it exceeds 30 parts by weight, absorption of active light on the exposed surface increases,
Internal photocuring tends to be inadequate. Further, since the photocurability of the exposed portion of the photosensitive thermoplastic resin layer (B) formed on the portion other than the inner surface of the recess becomes insufficient, the portion can be removed by the development described later, so that the component (c) The compounding amount of can be adjusted appropriately.

In addition, the (B) photosensitive thermoplastic resin layer in the present invention is a photosensitive resin composition layer (A) and a photosensitive thermoplastic resin layer (B) are
Being able to develop using the same developer,
It is preferable because the number of steps can be reduced. 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 which constitutes the photosensitive thermoplastic resin layer (B) soluble in water or an aqueous alkaline solution include:
Polyvinyl alcohol resin (hydrolyzate of polyacrylic acid ester or polymethacrylic acid ester, hydrolyzate of polyvinyl acetate, hydrolyzate of copolymer of ethylene and vinyl acetate, copolymerization of ethylene and acrylic acid ester) Hydrolyzate of polymer, Hydrolyzate of copolymer of vinyl chloride and vinyl acetate, Hydrolyzate of copolymer of styrene and acrylic acid ester or methacrylic acid ester, vinyl toluene and acrylic acid ester or methacrylic acid ester Hydrolysates of copolymers with), water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polyvinylpyrrolidone, unsaturated carboxylic acids and unsaturated copolymerizable with them Resin having a carboxyl group obtained by copolymerizing monomers Etc., 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 copolymer obtained by copolymerizing (A) a vinyl monomer which can be used in the film-forming polymer (A) constituting the photosensitive resin composition layer. And the like are preferably used. The weight average molecular weight of the resin having a carboxyl group obtained by copolymerizing an unsaturated carboxylic acid and an unsaturated monomer copolymerizable therewith is preferably 5,000 to 300,000, 20 It is more preferable to set it as 1,000 to 150,000. When the weight average molecular weight is less than 5,000,
When it is used as a photosensitive element, the film formability and flexibility tend to decrease, and when it exceeds 300,000, the developability tends to decrease.

The (B) photosensitive thermoplastic resin layer soluble in an alkaline aqueous solution is used as an unsaturated carboxylic acid and an unsaturated monomer copolymerizable therewith so that it can be developed by various known developing solutions. The carboxyl group content (which can be defined by the acid value (mgKOH / g)) of the resin having a carboxyl group obtained by copolymerizing the monomer can be appropriately adjusted. For example, when developing with an alkaline aqueous solution such as sodium carbonate or potassium carbonate, the acid value is 9
It is preferably set to 0 to 260. If the acid value is less than 90, development tends to be difficult, and if it exceeds 260, developer resistance tends to decrease. In the case of developing using an aqueous developer comprising water or an aqueous alkali solution and one or more organic solvents, the acid value is preferably from 16 to 260. 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 property of the (B) photosensitive thermoplastic resin layer, a plasticizer is added to the resin constituting the (B) photosensitive thermoplastic resin layer. can do. As the plasticizer, polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate,
Tricresyl phosphate, cresyl diphenyl phosphate, biphenyl diphenyl phosphate, and the like.

The photosensitive thermoplastic resin layer (B) in the present invention preferably has a viscosity at 100 ° C. of 1 to 1 × 10 ⁷ Pa · sec, and 2 to 1 × 10 ⁶ Pa · sec. More preferably, it is particularly preferably ⁵ to 1 × 10 ⁵ Pa · sec, and most preferably 10 to 1 × 10 ⁴ Pa · sec. If the viscosity at 100 ° C. is less than 1 Pa · sec, the viscosity at room temperature becomes too low to form a photosensitive element, so that (B) the photosensitive thermoplastic resin layer tends to exude from the edges due to flow. Therefore, the film formability tends to decrease. Moreover, when it exceeds 1 × 10 ⁷ Pa · sec,
Formability of the (A) photosensitive resin composition layer on the inner surface of the concave portion of the substrate having the irregularities described below tends to decrease.

The (B) photosensitive thermoplastic resin layer in the present invention is made into a uniform solution by dissolving or mixing it in a solvent that dissolves the resin constituting the resin, and a knife is formed on the support film described above. Coating method, roll coating method,
Spray coating, gravure coating, bar coating,
Coating using a known coating method such as a curtain coating method,
A film can be formed by drying. Examples of the solvent (B) for dissolving the resin forming the photosensitive thermoplastic resin layer include water, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, γ-butyl lactone, N-methylpyrrolidone. , Dimethylformamide, tetramethyl sulfone, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, chloroform, methylene chloride, methyl alcohol, ethyl alcohol and the like. These are used alone or in combination of two or more.

The thickness of the (B) photosensitive thermoplastic resin layer in the present invention is not particularly limited, but is preferably 10 to 200 μm from the viewpoint of embedding in the space of the PDP substrate, and the like. It is more preferable that the thickness is 20 to 100 μm. Further, a peelable cover film can be further laminated on the (B) photosensitive thermoplastic resin layer in the present invention. As the cover film, polyethylene, polypropylene, polyethylene terephthalate,
Examples thereof include polycarbonate and the like, in which the adhesive force between the cover film and the (B) photosensitive thermoplastic resin layer is smaller than the adhesive force between the support film and the (B) photosensitive thermoplastic resin layer. preferable. The (B) photosensitive thermoplastic resin layer thus formed into a film can be wound in a roll and can be stored.

Hereinafter, each step of the method for manufacturing a phosphor pattern of the present invention will be described in detail with reference to FIGS. 4 and 5. 4 and 5 are schematic diagrams showing each step of the method for manufacturing a phosphor pattern of the present invention.

[(I) On a substrate having irregularities, (A)
(D) In a state where the photosensitive thermoplastic resin layer (B) is disposed on the photosensitive resin composition layer containing the phosphor,
(B) Step of Thermocompression Bonding Layer] A state in which the (A) photosensitive resin composition layer 6 of the present invention is laminated on the PDP substrate 1 (substrate having irregularities) on which the barrier ribs 2 are formed is illustrated. 4 (I). In FIG. 4 (I), as a method for laminating the (A) photosensitive resin composition layer 6 on the PDP substrate 1 on which the barrier ribs 2 are formed, for example, the above-mentioned photosensitive element is used for laminating. Etc.

When a photosensitive element is used, if a cover film is present on the photosensitive element, after removing the cover film, the surface of the PDP substrate 1 on which the barrier ribs 2 are formed is (A) photosensitive. The resin composition layer 6 can be laminated by pressure bonding with a pressure bonding roll or the like so that the resin composition layer 6 contacts. The crimping pressure at this time is a gauge pressure (atmospheric pressure 1 atm is 0), preferably 1 × 10 ² to 1 × 10 ⁷ Pa, and preferably 5 × 10 ^{2 to} 5 × 10 ⁶ Pa. It is more preferable that the pressure is 1 × 10 ⁴ to 1 × 10 ⁶ Pa. If the pressure bonding pressure is less than 1 × 10 ² Pa, the (A) photosensitive resin composition layer 6 tends not to adhere sufficiently to the PDP substrate, and if it exceeds 1 × 10 ⁷ Pa, the PDP substrate Barrier ribs tend to be destroyed.

Further, in order to further improve (A) the embedding ability of the photosensitive resin composition layer 6 into the space, the surface of the pressure-bonding roll is made of a flexible material such as rubber or plastic. You can also do it. Note that the thickness of the layer made of a material having high flexibility is preferably 200 to 400 μm.

Further, in order to further improve (A) the embeddability of the photosensitive resin composition layer 6 into the space, the barrier rib 2 of the PDP substrate 1 is formed while heating the photosensitive element with a heating roll or the like. It is also possible to press-bond to the surface and laminate. 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 this heating temperature is lower than 10 ° C, the (A) photosensitive resin composition layer 6 tends to be unable to sufficiently adhere to the PDP substrate, and if it exceeds 130 ° C, the (A) photosensitive resin composition layer 6 Have a tendency to heat cure. In addition, the crimping pressure at the time of thermocompression bonding is 1 × in gauge pressure (normal pressure 1 atm is 0).
It is preferably 10 ² to 1 × 10 ⁷ Pa, and 5 × 10 ²
˜5 × 10 ⁶ Pa, more preferably 1 × 10 ⁴ ˜
It is particularly preferable that the pressure is 1 × 10 ⁶ Pa. If the pressure bonding pressure is less than 1 × 10 ² Pa, the (A) photosensitive resin composition layer 6 tends to be unable to sufficiently adhere to the PDP substrate,
If it exceeds 1 × 10 ⁷ Pa, the barrier ribs of the PDP substrate tend to be destroyed.

If the photosensitive element is heated as described above, it is not necessary to preheat the substrate for PDP having the barrier rib formed thereon, but (A) the filling property of the photosensitive resin composition layer 6 into the space is improved. From the point of further improvement, P
It is preferable to perform a pre-heat treatment on the DP substrate. further,
For the same purpose, the above-mentioned operations of the pressure bonding and the heat pressure bonding can be performed under a reduced pressure of 5 × 10 ⁴ Pa or less. Also, after the lamination is completed in this manner, in the range of 30 to 150 ° C,
Heating can be performed for 1 to 120 minutes. At this time, the support film can be removed as necessary.

(A) On the photosensitive resin composition layer 6,
FIG. 4 shows a state in which (B) the photosensitive thermoplastic resin layer 7 is arranged and (A) the photosensitive resin composition layer 6 and (B) the photosensitive thermoplastic resin layer 7 are laminated while being thermocompression bonded. II). In FIG. 4 (II), (A) photosensitive resin composition layer 6
As a method of disposing (B) the photosensitive thermoplastic resin layer 7 on the above and performing thermocompression bonding, for example, it is supported on the (A) photosensitive resin composition layer 6 in the state of FIG. 4 (I). If a body film is present, after removing the support film,
On the (A) photosensitive resin composition layer 6, the (B) photosensitive thermoplastic resin layer 7 (when a cover film is present, after removing the cover film) is arranged, and a heating roll is provided. Examples of the method include thermocompression bonding with No. 8 and the like.

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 (A) photosensitive resin composition layer 6 into the space of the PDP substrate tends to decrease, and if the heating temperature exceeds 130 ° C, the (A) photosensitive resin composition. Layer 6 tends to heat cure. In addition, the pressure for heating and pressure bonding is a gauge pressure (normal pressure 1 atm is 0).
Therefore, it is preferably 1 × 10 ⁴ to 1 × 10 ⁷ Pa, and 2
More preferably, it is from 10 ^{4 to} 5 × 10 ⁶ Pa, and 4 ×
Particularly preferably, it is 10 ⁴ to 1 × 10 ⁶ Pa. If this pressure is less than 1 × 10 ⁴ Pa, the embedding property of the (A) photosensitive resin composition layer 6 into the space of the PDP substrate tends to decrease, and if it exceeds 1 × 10 ⁷ Pa, it is for PDP. The barrier ribs of the substrate tend to break.

(B) If the photosensitive thermoplastic resin layer 7 is heated as described above, it is not necessary to preheat the PDP substrate on which the (A) photosensitive resin composition layer 6 is laminated. From the viewpoint of further improving the embedding property of the photosensitive resin composition layer 6 (A) into the space, it is preferable to preheat the PDP substrate on which the photosensitive resin composition layer 6 (A) is laminated. The preheating temperature at this time is preferably 30 to 130 ° C., and the preheating time is preferably 0.5 to 20 minutes. Further, in order to further improve the embedding property of the photosensitive resin composition layer 6 (A) into the space, the surface of the pressure-bonding roll may be made of a material having a high flexibility such as rubber or plastic. it can. Note that the thickness of the layer made of a material having high flexibility is preferably 200 to 400 μm.

Further, for the same purpose, the above-mentioned press bonding and heat pressing can be performed under reduced pressure of 5 × 10 ⁴ Pa or less. After the lamination is completed, 30 to 150 ° C
Can be heated for 1 to 120 minutes. At this time, if a support film is present on the (B) photosensitive thermoplastic resin layer 7, the support film may be removed as necessary. In this way, the (A) photosensitive resin composition layer 6 can be uniformly formed on the inner surface of the recess of the PDP substrate.

In the step (I) of the present invention,
Two layers of (A) the photosensitive resin composition layer 6 and (B) the photosensitive thermoplastic resin layer 7 may be laminated while thermocompression bonding at the same time. As the thermocompression bonding conditions when the two layers are thermocompressed at the same time, the conditions for thermocompressing the (B) photosensitive thermoplastic resin layer 7 can be used.

[(II) Step of Imagewise Irradiating Actinic Rays with Oxygen-Containing Gas Present on Layer (B)] Oxygen-Containing Gas (B) Photosensitive Thermoplastic Resin Layer 7 FIG. 4 (III) shows a state in which the actinic ray 11 is imagewise irradiated in the state of being present on the upper surface. In this step, (B) the actinic ray 11 needs to be imagewise irradiated in a state where a gas containing oxygen is always present on the photosensitive thermoplastic resin layer 7.
As a method thereof, for example, in a state where the (B) photosensitive thermoplastic resin layer 7 is in direct contact with the air or the like, a spacer 9 or the like is sandwiched on the (B) photosensitive thermoplastic resin layer 7 to form a negative film. , A negative glass, a positive film, a positive glass, or the like, and the actinic ray 11 is imagewise irradiated through the photomask 10. Further, if the (B) photosensitive thermoplastic resin layer 7 and the photomask 10 are not brought into close contact with each other so that oxygen is constantly replenished while the (B) photosensitive thermoplastic resin layer 7 is in contact with oxygen, (B) The actinic ray 11 may be imagewise irradiated in a state where the photomask 10 is directly placed on the photosensitive thermoplastic resin layer 7 without sandwiching the spacer 9 or the like.

At this time, (B) the photosensitive thermoplastic resin layer 7
In the case where a support film is present on the above, the exposed portion of the (A) photosensitive resin composition layer 6 and the exposed portion of the (B) photosensitive thermoplastic resin layer 7 which are formed other than the inner surface of the concave portion are treated with oxygen. Therefore, the photocurability becomes insufficient, and in order to remove the unnecessary portion by the development described later, it is necessary to irradiate the actinic ray 11 imagewise after removing the support film. However, only when the support film is a film having oxygen permeability, the actinic rays 11 can be imagewise irradiated in a state where the support films are laminated. Similarly, the exposed portion of the (A) photosensitive resin composition layer 6 and the exposed portion of the (B) photosensitive thermoplastic resin layer 7 formed on the surface other than the inner surface of the recess have insufficient photocurability due to oxygen. It is preferable that the exposure amount of the actinic ray 11 is appropriately adjusted so that it can be removed by the development described later.

Thus, on the inner surface of the recess, the photocured (A) photosensitive resin composition layer and the photocured (B) were formed.
The photosensitive thermoplastic resin layer 7 is formed, and the photocurability is insufficient except for the inner surface of the recess (A) the photosensitive resin composition layer and the photocurability is insufficient (B) A thermoplastic resin layer is formed.

As the actinic ray 11, a known actinic light source can be used, for example, carbon arc, mercury vapor arc,
Light emitted from xenon arc or the like can be used. Since the photoinitiator sensitivity is usually maximum in the UV region, the actinic light source in that case should be one that effectively emits UV light. When the photoinitiator is sensitive to visible light, for example, 9,10-phenanthrenequinone or the like, visible light is used as the active light 9, and the light source is as described above. In addition, a photo flood bulb, a sun lamp, and the like can be used.

[(III) Step of Removing Unnecessary Portion by Development] A state in which the unnecessary portion is removed by development is shown in FIG. 5 (IV). In FIG. 5 (IV), 6'denotes a photosensitive resin composition layer after photocuring, and 7'denotes a photosensitive thermoplastic resin layer after photocuring. In FIG. 5 (IV), as a developing method, for example, after the state of FIG. 4 (III), if a support film is present on the (B) photosensitive thermoplastic resin layer 7, this is After removal, spraying with a known developer such as an alkaline aqueous solution, an aqueous developer, an organic solvent,
Examples include a method of performing development by a known method such as rocking dipping, brushing, and scraping to remove unnecessary portions.

When removing the unnecessary portion, first, (A)
After removing (B) the photosensitive thermoplastic resin layer 7 by dissolution using water, an alkaline aqueous solution, a semisolvent aqueous solution, a semisolvent alkaline aqueous solution, an organic solvent or the like which does not dissolve the photosensitive resin composition layer 6, the development The liquid may be used to remove the unnecessary part of the (A) photosensitive resin composition layer 6, and the (B) photosensitive thermoplastic resin layer 7 may be the above-mentioned (A) photosensitive resin composition. When the layer 6 and the (B) photosensitive thermoplastic resin layer 7 can be developed using the same developing solution, the (A) photosensitive resin composition layer 6 is used by using the developing solution. It is also possible to remove the unnecessary portion and (B) the photosensitive thermoplastic resin layer 7 in one step. Further, (A) the photosensitive resin composition layer 6
As a method of removing the unnecessary portion of (1) and the unnecessary portion of (B) the photosensitive thermoplastic resin layer 7, it is also possible to carry out dry development individually or in one step.

In the step (III) of the present invention, the photocurable resin composition layer and the light-curing resin composition layer (A) having insufficient photocurability other than the inner surface of the recess formed by the step (II) are used. The (B) photosensitive thermoplastic resin layer having insufficient curability is an unnecessary portion and needs to be removed by development (also referred to as film slippage). The developing time and the developing temperature at this time can be appropriately adjusted so that unnecessary portions can be removed. The developing time is the minimum developing time of (A) the photosensitive resin composition layer 6 ((A) P of the photosensitive resin composition layer.
After embedding in the space of the DP substrate, the time is preferably 1 to 10 times the shortest time for removing the layer (A) by development, and the development temperature is 10 to 60 ° C. preferable. If the development time is less than the minimum development time, the residual development tends to occur, and if the development time exceeds 10 times the minimum development time, the necessary portion of the (A) photosensitive resin composition layer 6 tends to be removed. is there. In addition, the development temperature is 10 ℃
If it is less than 60 ° C, the developing property tends to be lowered, and if it exceeds 60 ° C, the developing solution resistance tends to be lowered.

As the base of the aqueous alkali solution, alkali hydroxides (lithium, sodium or potassium hydroxides, etc.), alkali carbonates (lithium, sodium or potassium carbonates or bicarbonates, etc.), alkali metal phosphates ( Potassium phosphate, sodium phosphate, etc.), alkali metal pyrophosphates (sodium pyrophosphate, potassium pyrophosphate, etc.), tetramethylammonium hydroxide, triethanolamine and the like, among which sodium carbonate, tetramethylammonium hydroxide And the like are preferred. PH of aqueous alkaline solution used for development
Is preferably 9 to 11, and the temperature thereof can be adjusted according to the developability of (A) the photosensitive resin composition layer 6 and (B) the photosensitive thermoplastic resin layer 7. . Further, a surfactant, a defoaming 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 developing solution include those containing water or an alkaline aqueous solution and one or more organic solvents.
Here, as the base of the alkaline aqueous solution, in addition to the above substances, for example, borax, sodium metasilicate, ethanolamine, ethylenediamine, diethylenetriamine,
2-amino-2-hydroxymethyl-1,3-propanediol, 1,3-diaminopropanol-2-morpholine, tetramethylammonium hydroxide and the like can be mentioned. 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 monoethyl ether, Diethylene glycol monobutyl ether and the like can be mentioned. These can be used alone or 2
Used in combination with more than one type. The concentration of the organic solvent is usually in the range of 2 to 90% by weight, and the temperature can be adjusted according to the developability. Also,
A small amount of a surfactant, a defoaming agent or the like can be mixed in the aqueous developer. Examples of the organic solvent developer used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. Water may be added to these organic solvents in the range of 1 to 20% by weight in order to prevent ignition.

In this way, the photocurability formed on the surface other than the inner surface of the recess is insufficient (A) the photosensitive resin composition layer and the photocurability is insufficient (B) the photosensitive thermoplastic resin. The unnecessary portion including the layer is removed by development, and the photosensitive resin composition layer 6 ′ after photocuring and the photosensitive thermoplastic resin layer (B) after photocuring are formed on the inner surface of the recess.

In the step (II) described above, the exposed portion of the (A) photosensitive resin composition layer 6 and the exposed portion of the (B) photosensitive thermoplastic resin layer 7 which are formed except the inner surface of the recess are
When the degree of insufficient photocurability by oxygen is not good, by performing this step ((III) step),
The state shown in FIG. 6 tends to occur. In this case, the photosensitive resin composition layer 6'after photocuring and the photosensitive thermoplastic resin layer 7 '(unnecessary portion) after photocuring remaining on the surface other than the inner surface of the recess can be completely removed by polishing or the like. . In addition, FIG. 6 is a schematic diagram showing a state after the step (III) is performed when the degree of insufficient photocurability by oxygen is not good in the step (II) of the present invention. In 6,
Reference numeral 13 is an unnecessary portion (where it is completely removed by polishing or the like).

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

[(IV) Step of Removing Unnecessary Part by Burning] FIG. 5 (V) shows a state in which the phosphor pattern after removing the unnecessary part by baking is formed. Note that FIG. 5 (V)
In, reference numeral 12 is a phosphor pattern. In FIG. 5 (V), the firing method is not particularly limited, and a known firing method can be used to remove unnecessary components other than the phosphor and the binder to form a phosphor pattern. The firing temperature at this time is preferably 350 to 800 ° C, and more preferably 400 to 600 ° C. The firing time is preferably from 3 to 120 minutes, more preferably from 5 to 90 minutes.

The method for producing the phosphor pattern of the present invention is as follows:
After repeating the steps (I) to (III) for each color to form a multicolored pattern including a photosensitive resin composition layer containing a phosphor that emits red, green and blue, (I)
In order to form a multicolor phosphor pattern by performing the step (V), it is possible to suppress film slippage (the photosensitive resin composition layer 6'after photocuring the first and second colors is Although exposed to a developing solution several times, these photocurable photosensitive resin composition layers 6 ′ are covered with the photocurable photosensitive thermoplastic resin composition layers 7 ′, and the photocurable photosensitive resin composition layers 6 ′ are directly exposed to the developing solution. Since it is not exposed to water, film slippage can be suppressed) and the number of steps can be reduced, which is preferable. In the present invention, the (A) photosensitive resin composition layer 6 containing each of the phosphors that emit red, blue and green alone can be performed in any order for each color of red, blue and green. .

The steps (I) to (III) in the present invention are repeated for each color to form a multicolor pattern including a photosensitive resin composition layer containing a phosphor that emits red, green and blue. The state in which this was done is shown in FIG. In FIG. 7, 6 '
a is a pattern for the first color, 6'b is a pattern for the second color, and 6'c is a pattern for the third color. FIG. 8 shows a state in which the multicolor phosphor pattern is formed by performing the step (IV) in the present invention. In FIG. 8, 12a is a phosphor pattern for the first color, 12b is a phosphor pattern for the second color, and 12c is a phosphor pattern for the third color.

[0086]

The present invention will be described below with reference to examples. Production Example 1 [Fabrication of Film-Providing Polymer (a-1)] A flask equipped with a stirrer, a reflux condenser, an inert gas inlet and a thermometer was charged with the composition shown in Table 1, and the content was 80
The temperature was raised to 0 ° C., and while maintaining the reaction temperature at 80 ° C. ± 2 ° C., as shown in Table 1 was uniformly added dropwise over 4 hours. After dropwise addition, stirring was continued at 80 ° C. ± 2 ° C. for 6 hours to obtain a film property imparting polymer (a-1) having a weight average molecular weight of 80,000 and an acid value of 130 mgKOH / g.

[0087]

[Table 1]

Production Example 2 [Production of Film-Providing Polymer (a-2)] In Production Example 1, 4 parts by weight of methacrylic acid, 86 parts by weight of methyl methacrylate and 10 parts of n-butyl methacrylate were prepared.
A film-forming polymer (a-2) having a weight average molecular weight of 80,000 and an acid value of 26 mgKOH / g was obtained in the same manner as in Production Example 1 except that parts by weight were replaced.

Production Example 3 [(A) Preparation of Photosensitive Element (A-1) Containing Photosensitive Resin Composition Layer] The materials shown in Table 2 were mixed for 15 minutes using a Likai machine to give a red photosensitive material. A resin composition solution was prepared.

[0090]

[Table 2]

The obtained solution was uniformly applied onto a polyethylene terephthalate film having a thickness of 20 μm,
The solvent was removed by drying for 10 minutes with a hot air convection dryer at 110 ° C to form a red (A) photosensitive resin composition layer. The thickness of the obtained photosensitive resin composition layer (A) after drying was 60 μm. Then, a polyethylene film having a thickness of 25 μm is laminated on the (A) photosensitive resin composition layer as a cover film to prepare a photosensitive element (A-1) containing the (A) photosensitive resin composition layer. did.

Production Example 4 [(A) Production of Photosensitive Element (A-2) Containing Photosensitive Resin Composition Layer] Production was carried out except that the material shown in Table 2 was used instead of the material shown in Table 2. In the same manner as in Example 3, a red (A) photosensitive resin composition layer was formed. The thickness of the obtained (A) photosensitive resin composition layer after drying was 60 μm.
Met.

[0093]

[Table 3]

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

Production Example 5 [(A) Production of Photosensitive Element (A-3) Containing Photosensitive Resin Composition Layer] Production was repeated except that the materials shown in Table 2 were used instead of the materials shown in Table 2. In the same manner as in Example 3, a blue (A) photosensitive resin composition layer was formed. The thickness of the obtained (A) photosensitive resin composition layer after drying was 60 μm.
Met.

[0096]

[Table 4]

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

Production Example 6 [(A) Production of Photosensitive Element (A-4) Containing Photosensitive Resin Composition Layer] Production was repeated except that the material shown in Table 2 was used instead of the material shown in Table 2. In the same manner as in Example 3, a green (A) photosensitive resin composition layer was formed. The thickness of the obtained (A) photosensitive resin composition layer after drying was 60 μm.
Met.

[0099]

[Table 5]

Then, in the same manner as in Production Example 3, a photosensitive element (A-4) containing the photosensitive resin composition layer (A) was prepared.

Production Example 7 [(B) Film Containing Photosensitive Thermoplastic Resin Layer (B-
Preparation of 1)] A resin solution containing the materials shown in Table 6
It is evenly coated on a polyethylene terephthalate film having a thickness of μm, and it is 1 with a hot air convection dryer at 80 to 110 ° C.
Distilled water was removed by drying for 0 minutes to form (B) a photosensitive thermoplastic resin layer. The thickness of the obtained (B) photosensitive thermoplastic resin layer after drying was 70 μm.

[0102]

[Table 6]

Next, a polyethylene film having a thickness of 25 μm is laminated as a cover film on the (B) photosensitive thermoplastic resin layer to form a film (B-1) containing the photosensitive thermoplastic resin layer (B-1). ) Was produced.

Production Example 8 [Production of Film (B-2) Containing Thermoplastic Resin Layer] The procedure of Production Example 7 was repeated except that the materials shown in Table 6 were used instead of the materials shown in Table 6. A thermoplastic resin layer was formed. The thickness of the obtained thermoplastic resin layer after drying was 70 μm.
m.

[0105]

[Table 7]

Then, in the same manner as in Production Example 7, a film (B-2) containing a thermoplastic resin layer was produced.

Photosensitive elements (A-1) and (A-) containing the photosensitive resin composition layer (A) obtained in Production Examples 3 to 6.
2), (A-3) and (A-4) and (B) the film (B-1) containing the photosensitive thermoplastic resin layer obtained in Production Examples 7 to 8 and the film containing the thermoplastic resin layer (B-
Regarding 2), the edge fusion property was evaluated by the following method, and the results are shown in Table 8.

[Edge Fusion Property] A photosensitive element including (A) a photosensitive resin composition layer having a length of 90 m, which is wound into a roll, (B) a film including a photosensitive thermoplastic resin layer, and a thermoplastic resin. The film containing the resin layer was stored at a temperature of 23 ° C. and a humidity of 60% Rh, and the appearance of seeping of the photosensitive layer and the resin layer from the side surface of the roll was visually evaluated for 6 months. The evaluation criteria are as follows. ◯: Good edge fusion property (no bleeding of the photosensitive layer even after 6 months) X: Poor edge fusion property (between the bleeding of the photosensitive layer during 6 months)

[0109]

[Table 8]

From Table 8, a photosensitive element (A) containing the photosensitive resin composition layer (A) obtained in Production Examples 3 and 6 was obtained.
-1), (A-2), (A-3) and (A-4) and (B) the film (B-1) containing the photosensitive thermoplastic resin layer obtained in Production Examples 7 to 8 and It can be seen that the films (B-2) containing the thermoplastic resin layer all have good edge fusion properties.

[Preparation of Phosphor Pattern] Example 1 [(I) Photosensitive resin composition layer containing (A) and (d) phosphor on a substrate having irregularities (B) Step of thermocompression bonding the layer (B) with the thermoplastic resin layer disposed thereon] PDP substrate (striped barrier ribs, opening width between barrier ribs 140 μm, barrier rib width 70 μm
m, the height of the barrier rib is 140 μm), while removing the polyethylene film, the photosensitive element (A-1) containing the photosensitive resin composition layer (A) obtained in Production Example 3 was removed on the side where the barrier rib was formed. Using a vacuum laminator (Hitachi Chemical Co., Ltd., trade name VLM-1 type), the heat shoe temperature is 30 ° C., the laminating speed is 0.5 m / min, the atmospheric pressure is 4000 Pa or less, and the pressure bonding pressure is 5 × 10. Laminated at ⁴ Pa.

Then, the polyethylene terephthalate film of the photosensitive element (A-1) containing the photosensitive resin composition layer (A) was peeled off, and the PDP substrate on which the photosensitive resin composition layer (A) was laminated was dried. In the pre-heating in 100 ° C for 10 minutes, the film (B-1) containing the (B) photosensitive thermoplastic resin layer obtained in Production Example 8 on the (A) photosensitive resin composition layer, While peeling off the polyethylene film,
Laminator (manufactured by Hitachi Chemical Co., Ltd., trade name HLM-30)
00 type), the laminating temperature is 110 ° C., the laminating speed is 0.5 m / min, and the pressure bonding is a gauge pressure (normal pressure 1).
Atm is 0) and laminated at 4 × 10 ⁵ Pa.

[(II) Step of imagewise irradiating with actinic rays in a state in which a gas containing oxygen is present on the layer (B)] Next, (B) a film containing a photosensitive thermoplastic resin layer ( B
In a state where a polyethylene terephthalate film of -1) is peeled off, a spacer having a thickness of 1 mm is sandwiched on the (B) photosensitive thermoplastic resin layer, and a gas containing oxygen is present on the (B) layer, Test photomask (transparent line width 150
(the line width to be masked is 480 μm), and an actinic ray was imagewise irradiated at 50 mJ / cm ² using an HMW-590 type exposure machine manufactured by Oak Manufacturing Co., Ltd.

[(III) Step of Removing Unnecessary Parts by Development] Next, after irradiation with actinic rays, the mixture was left at room temperature for 1 hour, and then spray-developed with a 1% by weight sodium carbonate aqueous solution at 30 ° C. for 150 seconds. . After development, it was dried at 80 ° C. for 10 minutes, irradiated with 3 J / cm ² of ultraviolet light using a Toshiba ultraviolet irradiation device manufactured by Toshiba Denshi Co., Ltd., and further heated in a dryer at 150 ° C. for 1 hour. .

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

[Evaluation of Phosphor Pattern] The cross section of the obtained phosphor pattern was visually observed with a stereoscopic microscope and SEM to evaluate the formation state of the phosphor pattern. The results are shown in Table 9. The evaluation criteria are as follows. ◯: The phosphor layer is uniformly formed on the inner surface of the recess (barrier rib wall surface and substrate surface) of the PDP substrate. X: The phosphor layer is not uniformly formed on the inner surface of the recess (barrier rib wall surface and substrate surface) of the PDP substrate.

Example 2 In Example 1, instead of the photosensitive element (A-1) containing the (A) photosensitive resin composition layer, a photosensitive element (A) containing the (A) photosensitive resin composition layer was used. -2) and (II
I) A phosphor pattern was formed in the same manner as in Example 1 except that the step of removing the unnecessary portion by development was changed as shown below, and the formation state of the obtained phosphor pattern was evaluated. The results are shown in Table 9. [(III) Step of removing unnecessary portion by development] 1% by weight
After developing with an aqueous solution of sodium carbonate,
Development was carried out using an aqueous solution of borax at 20% by weight and butyl carbitol at 20% by weight.

Example 3 In Example 1, instead of the photosensitive element (A-1) containing the photosensitive resin composition layer (A), a photosensitive element (A) containing the photosensitive resin composition layer (A) was used. A phosphor pattern was formed in the same manner as in Example 1, except that
The state of formation of the obtained phosphor pattern was evaluated, and the results are shown in Table 9.

Example 4 Instead of the photosensitive element (A-1) containing the photosensitive resin composition layer (A) in Example 1, a photosensitive element (A) containing the photosensitive resin composition layer (A) was used. A phosphor pattern was formed in the same manner as in Example 1, except that
The state of formation of the obtained phosphor pattern was evaluated, and the results are shown in Table 9.

Comparative Example 1 A phosphor pattern was formed in the same manner as in Example 1 except that the film (B-1) containing the photosensitive thermoplastic resin layer (B) in Example 1 was not used. Then, the formation state of the obtained phosphor pattern was evaluated, and the results are shown in Table 9.

Comparative Example 2 In the same manner as in Example 1, except that the film (B-1) containing the photosensitive thermoplastic resin layer (B) was replaced with the film (B-2) containing a thermoplastic resin layer. A phosphor pattern was formed in the same manner as in Example 1, and the formation state of the obtained phosphor pattern was evaluated. The results are shown in Table 9.

Comparative Example 3 In Example 1, except that the step of imagewise irradiating with actinic rays in the state where the gas containing oxygen (II) was present on the layer (B) was changed as shown below. In the same manner as in Example 1, a phosphor pattern was formed, the formation state of the obtained phosphor pattern was evaluated, and the results are shown in Table 9. [(II) Step of imagewise irradiating with actinic rays in a state where a gas containing oxygen is present on the layer (B)] (B) of a film (B-1) containing a photosensitive thermoplastic resin layer On the polyethylene terephthalate film without peeling off the polyethylene terephthalate film, a test photomask (transparent line width: 150 μm, masked line width: 480
(Hmw) manufactured by Oak Manufacturing Co., Ltd. without causing the gas containing oxygen to exist on the layer (B).
Image was irradiated with an actinic ray at 100 mJ / cm ² using a -590 type exposure machine.

[0123]

[Table 9]

[Preparation of Multicolor Phosphor Pattern] Example 5 Using the substrate on which the red pattern of the first color is obtained, which is obtained by performing the steps (I) to (III) in Example 1. The steps (I) to (III) in Example 3 are performed,
A second-color blue pattern was formed, and then the steps (I) to (III) in Example 4 were performed to form a third-color green pattern to prepare a multicolor pattern. The state of the resulting multi-colored film slippage was confirmed by a stereoscopic microscope and SE.
As a result of visual observation with M, no film slippage occurred. Next, the obtained multicolor pattern was subjected to the step (IV) in Example 1 to prepare a multicolor phosphor pattern. The obtained multicolor phosphor pattern is
Using the DAX PV9900 type “energy dispersive X-ray analyzer (XMA)” (accelerating voltage 20 kV), the composition of the phosphor was measured for each color, and the presence or absence of color mixing was confirmed. There wasn't.

Comparative Example 4 In Example 5, except that the film (B-1) containing a photosensitive thermoplastic resin layer (B) was replaced with a film (B-2) containing a thermoplastic resin layer. A multicolor pattern was prepared in the same manner as in Example 5, and the film slippage of the obtained multicolor pattern was observed in the same manner as in Example 5, as a result,
Membrane slip had occurred. Further, the obtained multicolored phosphor pattern was prepared in the same manner as in Example 5 to prepare a multicolored phosphor pattern, and the obtained multicolored phosphor pattern was prepared in the same manner as in Example 5 to determine whether or not there is color mixing. As a result, the mixed color was observed.

From the results of Table 9, Comparative Example 1 in which (B) the film containing the photosensitive thermoplastic resin layer was not used,
(B) Formability of a phosphor pattern in a space (inner surface of a recess) of a PDP substrate (a barrier rib surface of the PDP substrate, as compared with Examples 1 to 4 using a film containing a photosensitive thermoplastic resin layer) And the embeddability on the substrate surface) is poor. Further, after embedding the (A) photosensitive resin composition layer and the (B) photosensitive thermoplastic resin layer in the space of the PDP substrate, a state in which a gas containing oxygen is present on the (B) layer is given. Comparative Example 3 in which actinic rays were imagewise irradiated without
Is a state in which a phosphor pattern is projected to other than the inner surface of the recess as compared with Examples 1 to 4 in which a gas containing oxygen is present on the (B) layer and imagewise irradiation with actinic rays is performed. (The state of FIG. 6) is obtained, and it can be seen that the phosphor pattern forming property is inferior.

From the above results, in Example 5 in which (B) the film containing the photosensitive thermoplastic resin layer was used, the phosphor pattern forming property (PDP) in the space (inner surface of the recess) of the PDP substrate for each color was determined. The embedding property on the barrier rib surface and the substrate surface of the substrate for use is good, and there is no film slippage.
When a multicolor phosphor pattern was formed, no color mixture occurred. Further, from Comparative Example 2 and Comparative Example 4 in which the film (B-2) including the thermoplastic resin layer was used instead of the film (B) including the photosensitive thermoplastic resin layer,
The formability of the phosphor pattern in the space of the PDP substrate (fillability on the barrier rib wall surface and space bottom of the PDP substrate) was good, but film slippage occurred and a multicolor phosphor pattern was formed. In some cases, it has been found that color mixing occurs.

[0128]

According to the method of manufacturing a phosphor pattern according to the first aspect of the present invention, the embedding property in a space of a substrate having projections and depressions such as a PDP substrate (containing the phosphor on the barrier rib wall surface and the substrate surface of the PDP substrate is contained. Formability of photosensitive resin composition layer)
In addition, it is possible to prevent color mixture and form a highly accurate and uniform shape phosphor pattern with a margin only on the inner surface of the recess. The method for manufacturing a phosphor pattern according to claim 2 has the effects of the method for manufacturing a phosphor pattern according to claim 1, and is excellent in workability and suppression of film slippage. The method for manufacturing a phosphor pattern according to claim 3 has the effects of the method for manufacturing a phosphor pattern according to claim 1 or 2, and is more excellent in workability. The method for manufacturing a phosphor pattern according to claim 4 has the effects of the method for manufacturing a phosphor pattern according to claim 1, 2 or 3, and is more excellent in workability. The method for manufacturing a phosphor pattern according to claim 5,
The effect of the method for producing a phosphor pattern according to claim 1, 2, 3 or 4 is exhibited, and the workability is further improved.

[Brief description of drawings]

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

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

FIG. 3 is a schematic diagram showing an inner surface of a recess to which the (A) photosensitive resin composition of the present invention is adhered.

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

FIG. 5 is a schematic view showing each step of the method for producing a phosphor pattern of the present invention.

FIG. 6 is a schematic diagram showing a state after performing step (III) in the step (II) of the present invention when the degree of insufficient photocuring by oxygen is not good.

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

FIG. 8 is a schematic diagram showing a state in which a multicolor phosphor pattern is formed.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Substrate 2 ... Barrier rib 3 ... Lattice discharge space 4 ... Stripe discharge space 5 ... Recess inner surface 6 ... Photosensitive resin composition layer 6 '... Photocurable photosensitive resin composition layer 6'a ... 1st color Pattern 6'b ... 2nd color pattern 6'c ... 3rd color pattern 7 ... Photosensitive thermoplastic resin layer 7 '... Photocurable photosensitive thermoplastic resin layer 8 ... Heating roll 9 ... Spacer 10 ... Photo Mask 11 ... Actinic ray 12 ... Phosphor pattern 12a ... First color phosphor pattern 12b ... Second color phosphor pattern 12c ... Third color phosphor pattern 13 ... Unnecessary part

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication H01J 9/227 H01J 9/227 C // C08F 20/20 MMV C08F 20/20 MMV (72) Invention Yumiko Wada 4-13-1, Higashimachi, Hitachi, Ibaraki Prefecture Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd. (72) Seiji Tai, 4-13-1, Higashimachi, Hitachi City, Ibaraki Hitachi Chemical Co., Ltd.

Claims (5)

[Claims] 1. (I) On a substrate having irregularities, (A)
(D) In a state where the photosensitive thermoplastic resin layer (B) is disposed on the photosensitive resin composition layer containing the phosphor,
(B) a step of thermocompression-bonding the layer, (II) a step of imagewise irradiating an actinic ray with a gas containing oxygen on the (B) layer, (III) removing unnecessary portions by development And a step of (IV) removing unnecessary components by firing, which is a method for producing a phosphor pattern. 2. After the steps (I) to (III) are repeated to form a multicolored pattern composed of a photosensitive resin composition layer containing a phosphor that emits red, green and blue, ( I
The method for producing a phosphor pattern according to claim 1, wherein the step V) is performed to form a multicolor phosphor pattern. 3. A photosensitive resin composition layer (A), (a) a film property imparting polymer, (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group at the end, and (c) irradiation with active light. 3. The method for producing a phosphor pattern according to claim 1, wherein a free radical is generated by the method described above, and the generated free radical contains a photoinitiator which is easily deactivated by oxygen and (d) the phosphor. 4. The (B) photosensitive thermoplastic resin layer comprises (e)
Thermoplastic resin, (f) photopolymerizable unsaturated compound having an ethylenically unsaturated group, and (g) light that generates free radicals by irradiation with active light, and the generated free radicals are easily deactivated by oxygen The method for producing a phosphor pattern according to claim 1, 2 or 3, which comprises an initiator. 5. The method according to claim 1, wherein the layer (A) and the layer (B) are developed using the same developing solution in the step (III) of removing the unnecessary portion by development. Method for manufacturing phosphor pattern.