JPH1062980A - Photosensitive resin composition, photosensitive element and production of phosphor pattern using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin compsn. excellent in stability, work efficiency, etc., even when heated under reduced pressure by incorporating a film property imparting polymer, a specified photopolymerizable unsatd. compd., a photoinitiator and a phosphor. SOLUTION: This photosensitive resin compsn. contains a film property imparting polymer, a photopolymerizable unsatd. compd. having ethylenic unsatd. groups at the terminals and having >=300 deg.C b.p. under 760mmHg, a photoinitiator generating free radicals when irradiated with active light and a phosphor as essential components. This photosensitive element consists of a layer 5 of the photosensitive resin compsn. and a substrate film 6. The layer 5 is put on a substrate 1 for PDP with formed barrier ribs 2. After evacuation and heating, the layer 5 is imagewise irradiated with active light under atmospheric pressure and the unnecessary part is removed by development. These processes are repeated to form a multicolored pattern contg. red, green and blue phosphors and then the objective multicolored phosphor pattern is formed by firing.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition, a photosensitive element, and a method for producing 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. The PDP has a flat front plate and a rear plate made of glass, which are arranged in parallel and opposed to each other, and both are held at a fixed interval by barrier ribs provided between the front plate and the rear plate. And discharges in a space surrounded by the barrier ribs. In such a space, a phosphor for display is applied, and the phosphor is caused to emit light by ultraviolet rays generated from the sealing gas by discharge, so that the light can be visually recognized by an observer.

Conventionally, a method of providing this phosphor is as follows.
A method of applying a slurry 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, dispersion failure due to precipitation of the phosphor is likely to occur, and when a liquid photosensitive resist is used for the slurry liquid, it is preserved by promoting a dark reaction and the like. It has disadvantages such as poor stability. Furthermore, since printing methods such as screen printing are inferior in printing accuracy, there is a problem that it is difficult to cope with a larger PDP in the future.

In order to solve these problems, a method using a photosensitive element containing a phosphor (also referred to as a photosensitive film) has been proposed (Japanese Patent Laid-Open No. Hei 6-273925).
No.). The method using a photosensitive element means that a photosensitive resin layer containing a phosphor of a photosensitive element comprising a photosensitive resin layer containing a phosphor and a support film is heat-pressed (laminated) on the PDP substrate. Embedded in a space, and then imagewise exposed to actinic light such as ultraviolet light by a photographic method using a negative film. Thereafter, the unexposed portions are removed with a developing solution such as an aqueous alkaline solution, and then unburned by baking. A necessary organic component is removed to form a phosphor pattern only in a necessary portion. Therefore, the 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]

The object of the present invention is to provide a photosensitive resin composition having excellent stability and workability even when heated under reduced pressure. The invention described in claim 2 provides a photosensitive resin composition having more excellent stability in addition to the effects of the invention described in claim 1. The third aspect of the present invention provides a photosensitive element having excellent stability, workability, and handleability even when heated under reduced pressure. According to the fourth aspect of the present invention, there is provided a method of embedding a substrate having irregularities such as a PDP substrate into a space (in a PDP substrate,
Phosphor pattern capable of forming a phosphor pattern having a uniform shape with high precision, excellent in dimensional accuracy and pattern shape, and excellent in dimensional accuracy and pattern shapeability. Is provided. The invention according to claim 5 provides a method of manufacturing a phosphor pattern which is more excellent in workability, in addition to the effects of the invention according to claim 4.

[0007]

The present invention relates to (a) a polymer having a film property, (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group at a terminal and having a boiling point (760 mmHg) of 300 ° C. or more; The present invention relates to a photosensitive resin composition comprising c) a photoinitiator that generates free radicals upon irradiation with active light, and (d) a phosphor. The present invention also relates to the photosensitive resin composition wherein the molecular weight of the component (b) is 400 or more.
The present invention also relates to a photosensitive element having a layer of the photosensitive resin composition and a support film for supporting the layer.

[0008] The present invention also provides (I) a step of placing the photosensitive resin composition layer of the photosensitive element on a substrate having irregularities, (II) a step of reducing pressure, and (III) a step of heating. (IV) a step of returning to atmospheric pressure, (V) a step of irradiating actinic rays imagewise, (VI) a step of removing unnecessary parts by development, and (VII) a step of removing unnecessary parts by firing. And a method for manufacturing a phosphor pattern. 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 (VI),
The present invention relates to a method for producing the phosphor pattern for forming a multicolor phosphor pattern by performing the step (VII).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive resin composition of the present invention comprises
(A) a film-imparting polymer, (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group at the terminal and having a boiling point (760 mmHg) of 300 ° C. or higher, and (c) light that generates free radicals upon irradiation with active light. It contains an initiator and (d) a phosphor as essential components.

As the polymer (a) for imparting film property in the present invention, a vinyl copolymer is preferable. Examples of the vinyl monomer used for producing the vinyl copolymer include:
Acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-acrylic acid
Propyl, n-propyl methacrylate, iso acrylate
-Propyl, iso-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, iso acrylate
-Butyl, iso-butyl methacrylate, acrylic acid sec
-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, decyl methacrylate, 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, acrylic acid Cyclohexyl, 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, acrylic acid 2 -Hydroxyethyl, 2-hydroxyethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, 2-chloroethyl acrylate , 2-chloroethyl methacrylate, 2-fluoroethyl acrylate, 2-fluoroethyl acrylic acid, acrylic acid 2-cyanoethyl methacrylate, 2-cyanoethyl, styrene, alpha-methyl styrene, vinyl toluene,
Vinyl chloride, vinyl acetate, N-vinylpyrrolidone, butadiene, isoprene, chloroprene, acrylamide,
Examples include methacrylamide, acrylonitrile, methacrylonitrile and the like. These are used alone or in combination of two or more.

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

Further, the layer of the photosensitive resin composition of the present invention is
(A) so that it can be developed with various known developers.
The carboxyl group content (defined by the acid value (mgKOH / g)) of the film imparting polymer can be appropriately adjusted. For example, when developing using an aqueous alkali solution such as sodium carbonate or potassium carbonate, the acid value is set to 90 to 90.
260 is preferable. If the acid value is less than 90, development tends to be difficult, and if it exceeds 260,
There is a tendency that the developer resistance (the property that the remaining pattern that is not removed by development and remains as a pattern is not affected by the developer) decreases. In the case of developing using an aqueous developer composed of water or an aqueous alkali 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,
If it exceeds 260, the developer resistance tends to decrease.
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 (b) having an ethylenically unsaturated group at the terminal and having a boiling point (760 mmHg) of 300 ° C. or higher in the present invention has a boiling point (760 mmHg) of 3 or more.
The boiling point (760 mmHg) is preferably 350 ° C. or higher, and is preferably 400 ° C. or higher, from the viewpoints of stability and workability when heated under reduced pressure. More preferably, it is the above. The upper limit of this boiling point (760 mmHg) is usually 600 ° C. The boiling point (760 mmHg) can be determined by using a boiling point conversion chart described as an appendix on page (95) issued by Kagaku Doujin, 1st edition, "To continue the experiment safely". . For example, conversion of an associative liquid (a liquid having a group that forms a hydrogen bond such as OH or NH) at 200 ° C. (760 mmHg) or higher can be performed by extrapolation on the graph of A (β).

The weight average molecular weight of the photopolymerizable unsaturated compound (b) having an ethylenically unsaturated group at the terminal and having a boiling point (760 mmHg) of 300 ° C. or more is not particularly limited, but is heated under reduced pressure. From the viewpoints of stability, workability, and the like in the case, it is preferably 400 or more, more preferably 500 or more, and particularly preferably 600 or more. The upper limit of the weight average molecular weight is usually 5,000
0.

The boiling point (760 mmHg) having an ethylenically unsaturated group at the terminal (b) in the present invention is 300.
Examples of the photopolymerizable unsaturated compound having a temperature of at least 100 ° C. include 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, and Y is a saturated or unsaturated hydrocarbon group, a heterocyclic residue, a polyalkylene glycol residue, or a general formula (II), which may have a substituent.

Embedded image (Wherein R ¹ and R ² represent a hydrogen atom, a methyl group, an ethyl group,
A propyl group or a trifluoromethyl group, m and n
Each independently represents an integer of from 1 to 20).

Examples of the substituent in Y in the general formula (I) include a halogen atom, a hydroxyl group, an amino group and a carboxyl group. As the hydrocarbon residue, a linear, branched or alicyclic alkane residue having 1 to 22 carbon atoms (methane residue, ethane residue, propane residue, cyclopropane residue, butane residue, isobutane residue, cyclobutane residue) Residue, pentane residue, isopentane residue, neopentane residue, cyclopentane residue, hexane residue, cyclohexane residue, heptane residue, cycloheptane residue, octane residue, nonane residue, decane residue, etc.) And aromatic ring residues (benzene residue, naphthalene residue, anthracene residue, biphenyl residue, terphenyl residue, etc.). Examples of the heterocyclic residue include a furan residue, a thiophene residue, a pyrrole residue, and an oxazole residue.
Examples include a thiazole residue, an imidazole residue, a pyridine residue, a pyrimidine residue, a pyrazine residue, a triazine residue, a quinoline residue, and a quinoxaline residue.

In the present invention, (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group at the terminal and having a boiling point (760 mmHg) of 300 ° C. or higher, specifically, the following photopolymerizable unsaturated compounds: You can select and use from among them. Examples of the monomer having one unsaturated bond include, for example, ester monomers of acrylic acid or methacrylic acid (polyethylene glycol acrylate (the number of ethylene oxide is 9 to 50), polyethylene glycol methacrylate (the number of ethylene oxide is 9 to 50) ), Methoxypolyethylene glycol acrylate (the number of ethylene oxide is 9 to 50), methoxypolyethylene glycol methacrylate (the number of ethylene oxide is 9 to 50)
50), methoxypolypropylene glycol acrylate (the number of propylene oxide is 7 to 40), methoxypolypropylene glycol methacrylate (the number of propylene oxide is 7 to 40), styrene-based monomer, polyolefin-based monomer, vinyl-based monomer, Nitrile monomers and the like can be mentioned.

As a monomer having two unsaturated bonds,
For example, polyethylene glycol diacrylate (the number of ethylene oxide is 9 to 50), polyethylene glycol dimethacrylate (the number of ethylene oxide is 9 to 5)
0), hexapropylene glycol diacrylate,
Hexapropylene glycol dimethacrylate, polypropylene glycol diacrylate (the number of propylene oxide is 7 to 40), polypropylene glycol dimethacrylate (the number of propylene oxide is 7 to 40)
), Polyethylene glycol polypropylene glycol diacrylate (total number of ethylene oxide and propylene oxide 7 to 50), polyethylene glycol polypropylene glycol dimethacrylate (total number of ethylene oxide and propylene oxide 7 to 50),
2,2-bis (4-acryloxydiethoxyphenyl)
Propane, 2,2-bis (4-methacryloxydiethoxyphenyl) propane, 2,2-bis (4-acryloxypolyethoxyphenyl) propane 2,2-bis (4-
Methacryloxypolyethoxyphenyl) propane (in the formula (II),

Embedded image (4 ≦ m + n ≦ 40)), bisphenol A diglycidyl ether diacrylate, bisphenol A diglycidyl ether dimethacrylate, trimethylhexamethylene diisocyanate / cyclohexanedimethanol /
Examples thereof include urethane diacrylate compounds such as a reaction product of 2-hydroxyethyl acrylate (2/1/2 molar ratio).

As a monomer having three unsaturated bonds,
For example, propylene oxide-modified trimethylolpropane trimethacrylate, alkyl-modified dipentaerythritol triacrylate and the like can be mentioned. Examples of the monomer having four unsaturated bonds include ditrimethylolpropane tetramethacrylate, alkyl-modified dipentaerythritol tetraacrylate, alkyl-modified dipentaerythritol tetramethacrylate, ethylene oxide-modified pentaerythritol tetraacrylate, and ethylene oxide-modified pentaerythritol tetraacrylate. Methacrylate and the like.

Examples of the monomer having five unsaturated bonds include, for example, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol monohydroxypentamethacrylate, and alkyl-modified diacrylate. And pentaerythritol pentaacrylate. Examples of the monomer having six unsaturated bonds include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. In any case, these monomers have a boiling point (760 mmHg) of 300 ° C. or higher,
Any monomer capable of undergoing radical polymerization by light irradiation may be used, and these monomers having an unsaturated bond may be used alone or in combination of two or more.

In the photosensitive resin composition of the present invention, it is necessary to remove unnecessary components by baking at the time of forming the phosphor pattern. Therefore, the boiling point (b) having an ethylenically unsaturated group at the terminal ( It is more preferable to use polyethylene glycol diacrylate and polyethylene glycol dimethacrylate having good thermal decomposability as the photopolymerizable unsaturated compound having a temperature of 760 mmHg) of 300 ° C. or higher.

Examples of (c) a photoinitiator which generates free radicals upon irradiation with actinic light include aromatic ketones (benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone) ), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1
-(4-morpholinophenyl) -butanone-1,2,2
-Dimethoxy-1,2-diphenylethan-1-one,
1-hydroxy-cyclohexyl-phenyl-ketone,
2-methyl-1- (4- (methylthio) phenyl) -2
Morpholinopropanone-1,2,4-diethylthioxanthone, 2-ethylanthraquinone, phenanthrenequinone, etc., benzoin ether (benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, etc.), benzoin (methyl benzoin, ethyl benzoin, etc.) , Benzyl derivatives (benzyldimethyl ketal, etc.), 2,4,5-triarylimidazole dimer (2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4 2,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer Mers, 2-
(P-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl)-
5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, etc., acridine derivatives (9-phenylacridine, 1,7-bis (9,9'- Acridinyl) heptane and the like. These are used alone or in combination of two or more.

Further, the photosensitive resin composition of the present invention needs to remove unnecessary components by baking at the time of forming a phosphor pattern. Therefore, among these photoinitiators, oxygen is inhibited with high sensitivity. 2-benzyl-
2-dimethylamino-1- (4-morpholinophenyl)
-Butanone-1 or 1,7-bis (9,9'-acridinyl) heptane is more preferred.

The phosphor (d) in the present invention is not particularly limited, and a phosphor mainly composed of an ordinary metal oxide can be used. As a red-colored phosphor, for example, Y ₂ O ₂
S: Eu, Zn ₃ (PO ₄ ) ₂ : Mn, Y ₂ O ₃ : Eu, YV
O ₄ : Eu, (Y, Gd) BO ₃ : Eu, γ-Zn ₃ (PO ₄ )
₂ : Mn, (ZnCd) S: Ag + In ₂ O _{3 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.

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

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

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

The amount of the component (c) in the present invention is as follows:
The amount is preferably 0.01 to 30 parts by weight based on 100 parts by weight of the total of the components (a) and (b).
More preferably, it is 1 to 20 parts by weight. When the amount is less than 0.01 part by weight, the sensitivity of the photosensitive resin composition containing the phosphor tends to be insufficient, and when the amount exceeds 30 parts by weight, the photosensitive resin composition containing the phosphor tends to be insufficient. The absorption of active light on the exposed surface of the object tends to increase, and the internal light curing tends to be insufficient.

The amount of the component (d) in the present invention is as follows:
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 preferred that the amount be 0 to 200 parts by weight. When the amount is less than 10 parts by weight, the luminous efficiency tends to decrease when light is emitted as PDP, and when the amount exceeds 300 parts by weight, the film formability decreases when the photosensitive element is used, Flexibility tends to decrease.

The photosensitive resin composition of the present invention contains polyethylene glycol diacrylate and / or polyethylene as the component (b) because it facilitates the removal of unnecessary components by baking during the production of the phosphor pattern. Glycol dimethacrylate is used, and the component (c) includes 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 or / and 1,7-bis (9,
It is more preferred to use 9'-acridinyl) heptane.

To the photosensitive resin composition of the present invention, a compound having a carboxyl group can be added in order to prevent long-term thickening and to improve storage stability. As the compound having a carboxyl group, for example, saturated fatty acids, unsaturated fatty acids, aliphatic dibasic acids, aromatic dibasic acids,
Examples thereof include 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 amount of the compound having a carboxyl group is 0.01 to 30 parts by weight per 100 parts by weight of the component (a).
It is preferable to use parts by weight. When the blending amount is 0.01
If the amount is less than 30 parts by weight, the effect of storage stability tends to decrease, and if it exceeds 30 parts by weight, sensitivity tends to be insufficient.

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

The amount of the dispersant used is not particularly limited, and is preferably 0.01 to 10 parts by weight per 100 parts by weight of the component (a).
It is preferably 0 parts by weight. If this usage is 0.0
If it is less than 1 part by weight, the effect of addition tends not to be exhibited,
If 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.

After the firing, the photosensitive resin composition of the present invention
In order to prevent (d) the phosphor from peeling off from the PDP substrate, a binder may be added. Examples of the binder include a low-melting glass, a metal alkoxide, and a silane coupling agent. These can be used alone or 2
Used in combination of more than one type. The amount of the binder used is not particularly limited, and is preferably 0.01 to 100 parts by weight based on 100 parts by weight of the component (d).
The content is more preferably 0.05 to 50 parts by weight, and 0.1 to 50 parts by weight.
It is particularly preferred that the amount be 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 of the present invention contains a dye, a color former, a plasticizer, a pigment, a polymerization inhibitor, a surface modifier,
A stabilizer, an adhesion-imparting agent, a thermosetting agent, and the like can be added as needed.

The photosensitive element of the present invention has a layer of the photosensitive resin composition of the present invention and a support film for supporting the layer. The photosensitive element of the present invention, by dissolving or mixing the components constituting the photosensitive resin composition of the present invention in a dissolvable or dispersible solvent, to form a uniformly dispersed solution, on the support film , Applied and dried.

As the support film in the present invention,
Chemically and thermally stable, and, furthermore, composed of a flexible substance, for example, polyethylene terephthalate, polycarbonate, polyethylene, polypropylene and the like, among them, polyethylene terephthalate, polyethylene is preferred, polyethylene terephthalate is preferred More preferred. Since the support film must be removable from the layer of the photosensitive resin composition later, or has been subjected to a surface treatment that makes removal impossible,
It must not be a material. The thickness of the support film is preferably 5 to 200 μm, and 10 to 10 μm.
More preferably, it is 0 μm.

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

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. Drying temperature is 60 ~
The temperature is preferably set to 130 ° C, and the drying time is 3 minutes to 1 minute.
Preferably, it is time.

The thickness of the layer of the photosensitive resin composition in the photosensitive element of the present invention is not particularly limited.
The thickness is preferably 00 μm, more preferably 20 to 120 μm, and particularly preferably 30 to 80 μm. If the thickness is less than 10 μm, the phosphor pattern after firing tends to be thin and the luminous efficiency tends to decrease. If the thickness exceeds 200 μm, the phosphor pattern after firing becomes thick and the emission area of the phosphor screen is reduced. As a result, the luminous efficiency tends to decrease.

The layer of the photosensitive resin composition in the photosensitive element of the present invention has a viscosity at 100 ° C. of 1 to 1 × 10 ⁷ P
a · sec, more preferably 2 to 1 × 10 ⁶ Pa · sec, particularly preferably ⁵ to 1 × 10 ⁵ Pa · sec, and 10 to 1 × 10 ⁴ Pa · sec. It is highly preferred that The viscosity at 100 ° C. is 1 Pa · sec.
If it is less than 3, when the viscosity at room temperature becomes too low to form a photosensitive element, the layer of the photosensitive resin composition tends to seep out from the end due to the flow, and the film-forming property tends to decrease. On the other hand, if it exceeds 1 × 10 ⁷ Pa · sec, the formability of the layer of the photosensitive resin composition on the inner surface of the concave portion of the substrate having irregularities described later tends to decrease.

A releasable cover film can be further laminated on the photosensitive resin composition layer in the photosensitive element of the present invention. Examples of the cover film include polyethylene, polypropylene, polyethylene terephthalate, and polycarbonate, and the adhesive strength between the cover film and the photosensitive resin composition layer is higher than the adhesive strength between the support film and the photosensitive resin composition layer. Is preferably smaller. The photosensitive element of the present invention thus obtained can be stored in a roll. In addition, the photosensitive element of the present invention may be a multilayer photosensitive element provided with a layer such as an oxygen shielding layer in addition to the layer of the photosensitive resin composition as long as the effects of the invention are not impaired.

The method for producing the phosphor pattern of the present invention comprises:
(I) a step of placing the photosensitive resin composition layer of the photosensitive element of the present invention on a substrate having irregularities, (II) a step of reducing pressure, (III) a step of heating, and (IV) a step of heating to atmospheric pressure. Returning step, (V) irradiating actinic rays imagewise, (VI)
The method includes a step of removing unnecessary portions by development and a step of (VII) a step of removing unnecessary portions by firing.

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

FIGS. 1 and 2 show a P having a barrier rib formed thereon.
A schematic diagram of an example of a 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,
Although a square shape, an elliptical shape, etc. are possible, FIGS.
Thus, a grid-like or stripe-like discharge space is formed. 1 and 2, a barrier rib 2 is formed on a substrate 1, and in FIG.
However, in FIG. 2, a stripe-shaped discharge space 4 is formed. The size of the discharge space is determined by the size and resolution of the PDP, and in the case of a grid-like discharge space as shown in FIG. 1, the vertical and horizontal lengths are typically 50 μm to 1 mm.
In a striped discharge space as shown in FIG.
μm to 1 mm.

Hereinafter, each step of the method for producing a phosphor pattern of the present invention will be described in detail with reference to FIGS. FIGS. 3 and 4 are schematic views showing an example of each step of the method for producing a phosphor pattern of the present invention.

[(I) Step of mounting the photosensitive resin composition layer of the photosensitive element of the present invention on a substrate having irregularities] FIG. 3I shows a state where the resin composition layer is placed. FIG. 3 (I) shows a photosensitive resin composition layer 5 of the photosensitive element of the present invention having a photosensitive resin composition layer 5 and a support film 6, and a PDP having barrier ribs 2 formed thereon.
1 shows a state of being placed on a substrate for use (substrate having irregularities) 1.

In the step (I), a method for mounting the photosensitive resin composition layer 5 on a substrate having irregularities is as follows.
For example, when a cover film is present on the photosensitive element having the photosensitive resin composition layer 5 on the PDP substrate 1 on which the barrier ribs 2 are formed, after removing the cover film, the PDP substrate 1 is removed. There is a method in which the photosensitive resin composition layer 5 is temporarily fixed so as to be in contact with the surface on which the barrier ribs 2 are formed, and is installed.

When the photosensitive resin composition layer 5 is mounted on the surface of the PDP substrate 1 on which the barrier ribs 2 have been formed, a description will be given later (I
I) In the step of depressurizing, it is preferable that the device is placed so as to leave an air passage through which air in the discharge space can be discharged. Due to this air passage, when vacuum evacuation is performed in the step (II), the photosensitive resin composition layer 5 is greatly swollen, and the thickness of the photosensitive resin composition layer 5 becomes uneven or wrinkles occur. The tendency can be prevented.

In the heating step (III) described later, the photosensitive resin composition layer 5 is placed so that the air passage can be closed by heating the photosensitive resin composition layer 5. Is preferred. In the step (III), if the air passage remains even after the photosensitive resin composition layer 5 is heated, in the step (IV) of returning to the atmospheric pressure described later, the photosensitive resin composition layer 5 There is a tendency that the embedding property of the PDP substrate into the space is reduced.

In the heating step (III) described below,
As a method of closing the air passage by heating the photosensitive resin composition layer 5, for example, as shown in FIG. Is formed so as to surround the barrier rib 2 by heating the photosensitive resin composition layer without any gap, and to form the photosensitive resin composition layer 5 into a barrier rib. 2 and a method of placing the device so as to cover a region 10 having no unevenness (or a region having few unevenness). FIG. 5 is a schematic view showing an example of a substrate having irregularities used in the method of manufacturing a phosphor pattern of the present invention.

If the barrier ribs 2 have air permeability, the P on which the barrier ribs 2 are formed under the condition that the above-mentioned air passage is left.
The photosensitive resin composition layer 5 can be placed on the DP substrate 1 by pressure bonding with a pressure roll or the like, or by heat pressing with a heating roll. For example,
As shown in FIG. 6, a region 1 of the PDP substrate 1 having no irregularities
0, a low tack film such as a polyethylene film 11 is installed adjacent to the end of the barrier rib 2;
When a cover film is present on the photosensitive element 12 having the photosensitive resin composition layer 5, after removing the cover film, the photosensitive resin composition layer is formed on the surface of the PDP substrate 1 on which the barrier ribs 2 are formed. 5 by pressing with a pressure roll 13 or the like, or by heating and pressing with a heating roll or the like, and removing the polyethylene film 11 to leave the air passage 14. FIG. 6 is a schematic diagram showing an example of a method of mounting a photosensitive element so as to leave an air passage using the substrate shown in FIG.

The pressure at the time of press bonding or thermocompression bonding is preferably set to 10 ⁷ Pa or less as a gauge pressure (atmospheric pressure is 0). When this pressure exceeds 10 ⁷ Pa, the barrier ribs of the PDP substrate tend to be broken. The heating temperature at the time of thermocompression bonding is preferably 150 ° C. or lower, more preferably 130 ° C. or lower. When the heating temperature exceeds 150 ° C., the photosensitive resin composition layer 5
Have a tendency to thermoset.

Further, the step (II) of reducing the pressure, which will be described later, may be performed first, and the photosensitive resin composition layer 5 may be placed on a substrate having irregularities in a reduced pressure state. In this case, there is no need to form an air passage as described above. For example, if a cover film is present in the photosensitive element 12 having the photosensitive resin composition layer 5, after removing the cover film, The photosensitive resin composition layer 5 can be pressure-bonded by a pressure roll 13 or the like, or can be heat-pressed by a heating roll or the like so that the photosensitive resin composition layer 5 is in contact with the surface of the PDP substrate 1 on which the barrier rib 2 is formed. The pressure at the time of pressure bonding or heat pressure bonding is preferably 10 ⁷ Pa or less as a gauge pressure (the atmospheric pressure is 0). When this pressure exceeds 10 ⁷ Pa, the barrier ribs of the PDP substrate tend to be broken. The heating temperature at the time of thermocompression bonding is preferably 150 ° C. or lower, more preferably 130 ° C. or lower. When the heating temperature exceeds 150 ° C., the photosensitive resin composition layer 5 tends to be thermally cured.

[(II) Step of Depressurizing] As a depressurizing method in the step of (II) depressurizing, for example, a depressurizing method using a vacuum vessel 15 shown in FIG. 7 can be mentioned. FIG. 7 shows the PDP substrate 1 on which the photosensitive resin composition layer 5 is mounted.
Is a schematic view showing a state in which is horizontally installed in a vacuum vessel 15, wherein 15 is a vacuum vessel, 16 is a vacuum pump, 17 is a vacuum exhaust valve, and 18 is a heating device. This vacuum vessel 1
5, the PDP substrate 1 on which the photosensitive resin composition layer 5 is placed is horizontally installed and sealed, and then the vacuum pump 16 is started, the vacuum exhaust valve 17 is opened, and the inside of the vacuum vessel 15 is opened. The air can be exhausted to reduce the pressure. After the pressure in the vacuum vessel 15 is set to a predetermined pressure, the vacuum exhaust valve 17 is closed, and then a heating step (III) described later can be performed. Although the shape of the vacuum vessel 15 is not particularly limited, a step (IV) of returning to atmospheric pressure is performed after a step (III) of heating, which will be described later, so that the PDP on which the photosensitive resin composition layer 5 is mounted is used. Heating device 18 for heating substrate 1
It is preferable to have

The method of placing the PDP substrate 1 on which the photosensitive resin composition layer 5 is placed in the vacuum vessel 15 is not particularly limited, but usually, the vacuum vessel 15 is placed so that the PDP substrate 1 is horizontal. It is installed in. At this time, the support film 6 existing on the photosensitive resin composition layer 5 is usually removed, but the operation can be performed in a state where the support film 6 is present.

The pressure in the vacuum vessel 15 after the pressure reduction is 500
The pressure is preferably from 5 to 5 Pa, more preferably from 200 to 10 Pa, and particularly preferably from 100 to 20 Pa.
When this pressure exceeds 500 Pa, the photosensitive resin composition layer 5
The embedding property of the PDP substrate 1 into the space tends to decrease, and if it is less than 5 Pa, it takes too much time to exhaust, and the working efficiency tends to decrease.

[(III) Heating Step] The heating method in the (III) heating step is not particularly limited. For example, a heating method such as a hot plate provided in the vacuum vessel 15 shown in FIG. And a method in which the PDP substrate 1 is placed and heated by heat transfer, and a method in which an infrared light source is provided in the vacuum vessel 15 and heated by radiation. The heating temperature is preferably from 10 to 150 ° C.,
To 130 ° C, more preferably 50 to 110 ° C
It is particularly preferred that If the heating temperature is less than 10 ° C., the embedding property of the photosensitive resin composition layer 5 into the space of the PDP substrate 1 tends to decrease, and if it exceeds 150 ° C., the photosensitive resin composition layer 5 tends to thermally cure. There is. The heating time is preferably 1 hour or less, more preferably 20 minutes or less, and particularly preferably 10 minutes or less. If the heating time exceeds one hour, the photosensitive resin composition layer 5 tends to be thermally cured.

[(IV) Step of Returning to Atmospheric Pressure] FIG. 3 (II) shows the state after the step (II) of reducing the pressure, the step of heating (III), and the step of (IV) returning to the atmospheric pressure. Was. (II) the step of reducing pressure, (III) the step of heating and (I)
V) By performing the process of returning to the atmospheric pressure, FIG. 3 (II)
As shown in the figure, the photosensitive resin composition layer 5 was
Can be embedded in the space. The space inside the PDP substrate 1 refers to the inner surface 19 of the concave portion where the photosensitive resin composition layer 5 of the present invention is adhered, as shown in FIG. 8, and in FIG. The inner surface 19 of the concave portion is indicated by oblique lines. Also, by changing the combination of the conditions such as the film thickness of the photosensitive element of the present invention, the above-mentioned heating temperature and pressure conditions, the photosensitive resin composition layer 5 of the present invention adheres to the state shown in FIG. It can also be done. FIG. 9 shows an example of the method for manufacturing a phosphor pattern of the present invention after the step (I), the step (II), the step (III) and the step (IV).

(IV) As a method of returning to the atmospheric pressure in the step of returning to the atmospheric pressure, for example, after the step of (III), the vacuum pump 16 is stopped, and the closed vacuum exhaust valve 17 is gently opened. By introducing air or the like, the inside of the vacuum container 15 can be returned to the atmospheric pressure. Vacuum container 15
The time from the start of introduction of air or the like to the inside until the atmospheric pressure is reached is preferably within 30 minutes, more preferably within 10 minutes, and particularly preferably within 5 minutes. If the time exceeds 30 minutes, the embedding property of the photosensitive resin composition layer 5 into the space of the PDP substrate 1 tends to decrease.

[(V) Step of irradiating actinic rays imagewise]
FIG. 3 (III) shows a state in which the actinic rays 8 are irradiated imagewise. In the step of FIG. 3 (III), a method of imagewise irradiating the actinic ray 8 is as follows. A photomask such as a negative film or a positive film is provided on the photosensitive resin composition layer 5 in the state of FIG. 3 (II). Via 7, it can be illuminated imagewise by actinic light 8. At this time, when a support film is present on the photosensitive resin composition layer 5, the active film 8 may be irradiated imagewise with the support film laminated,
Further, the actinic ray 8 may be irradiated imagewise after the support film is removed.

The transmission width of the actinic rays 8 of the photomask 7 is usually the opening width of the concave portion of the PDP substrate, but the process (I), the process (II), and the process (III) After the steps (IV) and (IV), when the layers are laminated as shown in FIG. 3 (II), the transmission width is the same as the opening width of the recess of the PDP substrate or the transmission width is wider than the opening width of the recess of the PDP substrate. The width is preferable from the viewpoint that the latitude of the positioning accuracy can be increased.

As the actinic ray 8, a known actinic light source can be used, and examples thereof include light generated from a carbon arc, a mercury vapor arc, a xenon arc, and the like.
Since the sensitivity of the photoinitiator is usually maximal in the ultraviolet region, the active light source in that case should be one that effectively emits ultraviolet light. When the photoinitiator is sensitive to visible light, for example, 9,10-phenanthrenequinone or the like, visible light is used as the active light 8 and the light source is as described above. In addition, a photo flood bulb, a sun lamp, and the like can be used.

[(VI) Step of Removing Unwanted Parts by Development] FIG. 3 (IV) shows a state where the unnecessary parts are removed by development. In FIG. 3 (IV), 5 'is a photosensitive resin composition layer after photo-curing. In the step of FIG. 3 (IV),
As a developing method, for example, after the state of FIG.
When a support film or the like is present on the photosensitive resin composition layer 5, after removing the support film or the like, using a known developer such as an aqueous alkali solution, an aqueous developer, or an organic solvent, for example,
A method in which development is performed by a known method such as spraying, rocking immersion, brushing, and scraping to remove unnecessary portions, and the like.

Examples of the base of the aqueous alkali solution include alkali hydroxides (such as hydroxides of lithium, sodium or potassium), alkali carbonates (such as carbonates or bicarbonates of lithium, sodium or potassium), and alkali metal phosphates (such as carbonates or bicarbonates). Potassium phosphate, sodium phosphate, etc.), alkali metal pyrophosphates (sodium pyrophosphate, potassium pyrophosphate, etc.), tetramethylammonium hydroxide, triethanolamine, etc., among which sodium carbonate, tetramethylammonium hydroxide And the like are preferred. PH of aqueous alkaline solution used for development
Is preferably 9 to 11, and the temperature can be adjusted according to the developability of the photosensitive resin composition layer 5. In addition, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating the development, and the like can be mixed in the aqueous alkali solution.

Examples of the aqueous developer include those comprising water or an aqueous alkali 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,
Examples thereof include 2-amino-2-hydroxymethyl-1,3-propanediol, 1,3-diaminopropanol-2-morpholine, and tetramethylammonium hydroxide. 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, And diethylene glycol monobutyl ether. These can be used alone or 2
Used in combination of 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, an antifoaming agent or the like can be mixed in the aqueous developer.

The organic solvent developer used alone includes, for example, 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ-butyrolactone, and the like. These organic solvents are used to prevent ignition.
Water may be added in a range of ２０20% by weight.

For the purpose of preventing the phosphor from deteriorating after the development, the base of the aqueous alkali solution remaining in the photosensitive resin composition layer 5 ′ after the photocuring is treated with an organic acid, an inorganic acid or an aqueous solution of these acids. Using, spraying, rocking dipping, brushing,
Acid treatment (neutralization treatment) by a known method such as scraping
can do. Examples of the acid include a saturated fatty acid,
Organic acids and inorganic acids such as unsaturated fatty acids, aliphatic dibasic acids, aromatic dibasic acids, aliphatic tribasic acids, and aromatic tribasic acids are exemplified.

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

The pH of the aqueous acid solution used for the acid treatment is preferably from 2 to 6, and the pH and temperature of the aqueous acid solution are controlled by adjusting the pH of the photosensitive resin composition layer 5 'containing the photocured phosphor and the PD.
It can be adjusted in accordance with the acid resistance (durability that does not deteriorate with acid) of the P substrate (substrate having irregularities). Further, after the acid treatment (neutralization treatment), a step of washing with water can be performed.

After development, ultraviolet irradiation or heating using a high-pressure mercury lamp or the like can be performed 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. At this time, the irradiation amount of the ultraviolet ray is usually 0.2 to 10 J / cm ² , and the irradiation can be accompanied by heating. The heating temperature is
The temperature is preferably 60 to 180 ° C, and 100 to 180 ° C.
C. is more preferable. The heating time is 15
It is preferable to set it for 90 minutes. Irradiation and heating of these ultraviolet rays may be performed separately from irradiation and heating, or either may be performed first.

[(VII) Step of Removing Unwanted Components by Firing] FIG. 4 (V) shows a state in which the phosphor pattern has been formed after the unnecessary components have been removed by firing. FIG. 4 (V)
In the above, 9 is a phosphor pattern. In the step of FIG. 4 (V), the firing method is not particularly limited, and a known firing method can be used to remove unnecessary substances other than the phosphor and the binder, thereby forming a phosphor pattern. . The firing temperature at this time is preferably from 350 to 800 ° C, more preferably from 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 a phosphor pattern of the present invention is characterized in that the method (I) according to the present invention is advantageous in that the number of steps can be reduced.
Steps (VI) to (VI) are repeated for each color to form a multicolor pattern made of a photosensitive resin composition containing a phosphor that emits red, green and blue colors. It is preferable to form a multicolor phosphor pattern.
In the present invention, the photosensitive resin composition layer 5 having each of the phosphors that emit red, blue, and green independently can be formed in any order for each of the red, blue, and green colors.

The steps (I) to (VI) in the present invention are repeated for each color to form a multicolor pattern made of a photosensitive resin composition containing a phosphor emitting red, green and blue colors. FIG. 10 shows the state after the completion. In FIG. 10, 5'a is the first color pattern, 5'b is the second color pattern, and 5'c is the third color pattern. FIG. 11 shows a state in which the multicolor phosphor pattern is formed by performing the step (VII) in the present invention. In FIG. 11, 9a is the first color phosphor pattern, 9b is the second color phosphor pattern, and 9c is the third color phosphor pattern.

In the method of manufacturing a phosphor pattern of the present invention, the steps (I) to (VII) of the present invention are repeated for each color to reduce red, It is preferable to form a multicolor phosphor pattern that emits green and blue light.

[0079]

The present invention will be described below with reference to examples. Production Example 1 [Preparation of film-imparting polymer (a-1)] 70 parts by weight of ethylene glycol monomethyl ether and 50 parts by weight of toluene were placed in a flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer. The temperature was raised to 80 ° C. under a nitrogen gas atmosphere, and while maintaining the reaction temperature at 80 ° C. ± 2 ° C., the materials shown in Table 1 were uniformly dropped over 4 hours.
Stirring was continued for 6 hours at a temperature of ± 2 ° C and a weight average molecular weight of 80,0.
00, a film-imparting polymer having an acid value of 130 mgKOH / g (a
-1) was obtained.

[0080]

[Table 1]

Example 1 [Preparation of solution (A-1) of photosensitive resin composition] The materials shown in Table 2 were mixed for 15 minutes using a raikai machine, and the solution of the photosensitive resin composition (A-1) was mixed. ) Was prepared.

[0082]

[Table 2]

Comparative Example 1 [Preparation of Solution (A-2) of Photosensitive Resin Composition] The materials shown in Table 3 were mixed for 15 minutes using a raikai machine to obtain a solution of the photosensitive resin composition (A-2). ) Was prepared.

[0084]

[Table 3]

Example 2 [Preparation of photosensitive element (i)] The solution (A-1) of the photosensitive resin composition obtained in Example 1 was uniformly spread on a polyethylene terephthalate film having a thickness of 20 µm. It was applied and dried with a hot air convection dryer at 110 ° C. for 10 minutes to remove the solvent, thereby forming a photosensitive resin composition layer. The thickness of the obtained photosensitive resin composition layer was 60 μm. Next, on this photosensitive resin composition layer, 25 μm
A polyethylene film having a thickness of m was laminated as a cover film to prepare a photosensitive element (i).

Comparative Example 2 [Preparation of photosensitive element (ii)] The solution (A-2) of the photosensitive resin composition obtained in Comparative Example 1 was uniformly spread on a polyethylene terephthalate film having a thickness of 20 µm. It was applied and dried with a hot air convection dryer at 110 ° C. for 10 minutes to remove the solvent, thereby forming a photosensitive resin composition layer. The thickness of the obtained photosensitive resin composition layer was 60 μm. Next, on this photosensitive resin composition layer, 25 μm
A m-thick polyethylene film was laminated as a cover film to produce a photosensitive element (ii).

The edge fusion properties of the photosensitive elements (i) and (ii) obtained in Example 2 and Comparative Example 2 were evaluated by the following methods. The results are shown in Table 4. [Edge fusion property] The photosensitive element (i) and the photosensitive element (ii) each having a length of 90 m wound up in a roll shape are stored at a temperature of 23 ° C and a humidity of 60% Rh,
Exudation of the photosensitive layer from the side of the roll was visually evaluated over a period of 6 months. The evaluation criteria are as follows. 〇: Good edge fusion property (no exudation of photosensitive layer even in 6 months) ×: Poor edge fusion property (thing exuded of photosensitive layer in 6 months)

[0088]

[Table 4] From the results in Table 4, the photosensitive elements (i) and (ii) produced in Example 2 and Comparative Example 2 had good edge fusion properties.

[Preparation of Phosphor Pattern] Example 3 [(I) Step of Placing Photosensitive Resin Composition Layer of Photosensitive Element on Substrate Having Irregularities] 200 × 200 × 3
In the center of the glass plate of 12 mm × 122.6 × 162.6 mm, grid-shaped barrier ribs (the opening width between the barrier ribs is 250 mm).
× 350 μm, barrier rib width 50 μm, barrier rib height 150 μm) The polyethylene film of the photosensitive element (i) cut into a size of 150 × 190 mm was peeled off on the side of the PDP substrate on which the barrier ribs were formed. After that, the photosensitive resin composition layer was brought into contact with the barrier rib, and the outer periphery of the region where the barrier rib was formed was 1 cm.
It was placed so as to cover the above width.

[(II) Step of Decompressing] Next, the polyethylene terephthalate film present on the photosensitive resin composition layer placed on the PDP substrate is peeled off, and put into a vacuum dryer equipped with a heating device. The pressure was reduced to 80 Pa at room temperature.

[(III) Heating Step and (IV) Step of Returning to Atmospheric Pressure] Then, under reduced pressure, the temperature is raised to 100 ° C. at a rate of 5 ° C./min and maintained at 100 ° C. for 1 minute. After that, the pressure was returned to the atmospheric pressure, whereby the photosensitive resin composition layer was brought into close contact with the inner surface of the concave portion.

[(V) Step of irradiating actinic rays imagewise]
Next, a test photomask was brought into close contact with the side of the PDP substrate on which the photosensitive resin composition layer was formed, and activated at 100 mJ / cm ² using an HMW-590 type exposure machine manufactured by Oak Manufacturing Co., Ltd. The light beam was illuminated imagewise.

[(VI) Step of Removing Unwanted Parts by Development] Next, after irradiating with actinic rays, the mixture was allowed to stand at room temperature for 1 hour, and then exposed to 1% by weight aqueous sodium carbonate solution at 30 ° C.
Spray developed for 50 seconds. After the development, the film was dried at 80 ° C. for 10 minutes, and irradiated with 3 J / cm ² of ultraviolet light using a Toshiba ultraviolet light irradiation device manufactured by Toshiba Electric Materials Co., Ltd.

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

[Evaluation of Phosphor Pattern] The cross section of the obtained phosphor pattern was visually observed with a stereoscopic microscope and an SEM to evaluate the formation state of the phosphor pattern. The results are shown in Table 5. The evaluation criteria are as follows. A: The phosphor pattern is uniformly formed in the space (on the barrier rib wall surface and the cell bottom surface) of the PDP substrate. X: The phosphor pattern was not formed in the space (on the barrier rib wall surface and the cell bottom surface) of the PDP substrate.

Example 4 [Step (I)] In the center of a 200 × 200 × 3 mm glass plate, stripe-shaped barrier ribs (opening width between barrier ribs: 194 μm, width of barrier ribs: 121.9 × 162.6 mm) After removing the polyethylene film of the photosensitive element (i) cut into a size of 150 × 190 mm on the side of the PDP substrate on which the barrier ribs are formed, on which the barrier ribs are formed, the photosensitive resin is formed. The substrate was placed so that the composition layer was in contact with the barrier ribs and the outer periphery of the region where the barrier ribs were formed was covered with a width of 1 cm or more.

[Steps (II) to (VII)] Next, in each of the steps (II) to (VII), the fluorescent light was A body pattern was formed. The state of formation of the obtained phosphor pattern was evaluated in the same manner as in Example 3, and the results are shown in Table 5.

Example 5 [Step (I)] In the center of a 200 × 200 × 3 mm glass plate, stripe-shaped barrier ribs (opening width between barrier ribs: 194 μm, barrier rib width: 121.9 × 162.6 mm) On the side of the PDP substrate on which the barrier ribs are formed, on the side of the PDP substrate on which the barrier ribs are formed (from 70 μm, the height of the barrier ribs is 150 μm), one end of the boundary of the barrier rib region formed by one end of the stripe of the barrier ribs to the end of the PDP substrate. A polyethylene film having a thickness of 100 μm was temporarily fixed to the region. Next, while peeling off the cover film of the photosensitive element (i), a laminator (Hitachi Chemical Industries, Ltd.)
Manufactured by HLM-3000 (trade name), a laminating temperature of 60 ° C., a laminating speed of 0.5 m / min, and a pressure of 2 × 10 ⁵ Pa. The film was removed.

[Steps (II) to (VII)] Next, in each of the steps (II) to (VII), the fluorescent light was A body pattern was formed. The state of formation of the obtained phosphor pattern was evaluated in the same manner as in Example 3, and the results are shown in Table 5.

Comparative Example 3 [Steps (I) to (VII)]
A phosphor pattern was formed in the space of the PDP substrate in the same manner as in Example 3 except that the photosensitive element (i) was replaced with the photosensitive element (ii). The evaluation was performed in the same manner as in Example 3, and the results are shown in Table 5.

[0101]

[Table 5]

From the results shown in Table 5, a photosensitive element (i) using the photosensitive resin composition of the present invention was prepared, and a photosensitive resin composition layer was formed on the inner surface of the concave portion using the photosensitive element (i). Phosphor pattern obtained by contact (Examples 3 to
5) was excellent in pattern formability. On the other hand, a photosensitive element (ii) using a photosensitive resin composition layer outside the scope of the present invention was prepared, and a phosphor pattern prepared using the photosensitive element (ii) (Comparative Example 3) Had poor pattern formability.

[0103]

The photosensitive resin composition according to the first aspect is excellent in stability, workability and the like even when heated under reduced pressure. The photosensitive resin composition according to the second aspect has the effect of the photosensitive resin composition according to the first aspect, and is more excellent in stability. The photosensitive element according to the third aspect has excellent stability, workability, and handleability even when heated under reduced pressure, and can be suitably used for forming a phosphor pattern. The method of manufacturing a phosphor pattern according to claim 4, is characterized in that the substrate having irregularities such as a PDP substrate has a burying property in a space (for a PDP substrate,
Excellent in the form of a photosensitive resin composition layer containing a phosphor on the barrier rib wall surface and on the bottom of the space), excellent in dimensional accuracy and pattern shape, and capable of forming a highly accurate and uniform phosphor pattern. The method for producing a phosphor pattern according to the fifth aspect has the effect of the method for producing a phosphor pattern according to the fourth aspect, and is excellent in workability.

[Brief description of the drawings]

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

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

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

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 diagram showing an example of a substrate having irregularities used in the method of manufacturing a phosphor pattern of the present invention.

FIG. 6 is a schematic view showing an example of a method of mounting a photosensitive element so as to leave an air passage using the substrate shown in FIG.

FIG. 7 is a schematic diagram showing a state in which a substrate having irregularities on which a photosensitive resin composition layer is placed is horizontally installed in a vacuum container.

FIG. 8 is a schematic view showing an inner surface of a concave portion in which a layer of the photosensitive resin composition according to the present invention is adhered.

FIG. 9 shows the step (I) and the step (II) in the present invention;
It is the schematic diagram which showed an example after completion | finish of the process of (III) and the process of (IV).

FIG. 10 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. 11 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 Grid-shaped discharge space 4 Striped discharge space 5 Photosensitive resin composition layer 5 'Photocured resin composition layer after photocuring 5'a First color pattern 5'b Second color pattern 5'c Third color pattern 6 Support film 7 Photomask 8 Actinic ray 9 Phosphor pattern 9a First color phosphor pattern 9b Second color phosphor pattern 9c Third color phosphor pattern 10 Uneven area 11 Polyethylene film 12 Photosensitivity Element 13 Crimping roll 14 Air passage 15 Vacuum container 16 Vacuum pump 17 Vacuum exhaust valve 18 Heating device 19 Inside recess

Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location G03F 7/38 501 G03F 7/38 501 7/40 501 7/40 501 H01J 9/02 H01J 9/02 F 9 / 227 9/227 C (72) Inventor Yumiko Wada 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Within Hitachi Chemical Co., Ltd.Ibaraki Research Laboratories (72) Inventor Seiji Tai 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture No.Hitachi Chemical Industry Co., Ltd.

Claims (5)

[Claims] 1. A (a) polymer having a film property, (b) a photopolymerizable unsaturated compound having a terminal ethylenically unsaturated group having a boiling point (760 mmHg) of 300 ° C. or higher, and (c) a liberation upon irradiation with actinic light. A radical-generating photoinitiator and (d)
A photosensitive resin composition comprising a phosphor. 2. The photosensitive resin composition according to claim 1, wherein the molecular weight of the component (b) is 400 or more. 3. A photosensitive element comprising a layer of the photosensitive resin composition according to claim 1 and a support film for supporting the layer. 4. The method of claim 1, wherein (I) placing the photosensitive resin composition layer of the photosensitive element according to claim 3 on a substrate having irregularities, (II) reducing pressure, and (III) heating.
(IV) a step of returning to atmospheric pressure, (V) a step of irradiating actinic rays imagewise, (VI) a step of removing unnecessary parts by development, and (VII) a step of removing unnecessary parts by firing. A method for producing a phosphor pattern. 5. The method according to claim 1, wherein each of the steps (I) to (VI) is repeated,
After forming a multicolor pattern composed of a photosensitive resin composition layer containing a phosphor that emits red, green and blue, (VII)
5. A multicolor phosphor pattern is formed by performing the above steps.
A method for producing the phosphor pattern as described above.