JPH1195420A - Production of rear surface plate for plasma display panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing a rear surface plate for a plasma display panel which does not give rise to the deterioration in phosphor luminance. SOLUTION: This process for producing the rear surface plate for the plasma display panel is constituted to include (I) a stage for forming a photosensitive resin compsn. layer contg. phosphors on a substrate for the plasma display panel formed with barrier ribs, (II) a stage for irradiating the photosensitive resin compsn. layer contg. the phosphors imagewise with active rays, (III) a stage for forming patterns by selectively removing the unnecessary parts of the photosensitive resin compsn. layer contg. the phosphors by development and (IV) a stage for forming the phosphor patterns by removing the unnecessary parts by baking from the patterns described above. In such a case, a developer contg. transition metal ions, sulfuric acid ions, sulfurous acid ions, nitric acid ions, nitrous acid ions, chlorine ions and chlorine respectively at contents of <500 ppm in weight concn. is used in (III) the process for forming the patterns by selectively removing the unnecessary parts of the photosensitive resin compsn. layer contg. the phosphors by development.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for manufacturing a back plate for a plasma display panel.

[0002]

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

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

[0004] In such a space, a phosphor for display is applied, and the phosphor is illuminated by ultraviolet rays generated from the sealed gas by discharge, so that the light can be visually recognized by an observer.

Conventionally, as a method of providing this phosphor, there are:
A method of applying a slurry liquid or paste in which phosphors of each color are dispersed by a printing method such as screen printing has been proposed, and is disclosed in JP-A-1-115027, JP-A-1-124929, and JP-A-1-124930. And JP-A-2-155142.

However, since the above-mentioned phosphor dispersion slurry is in a liquid state, poor dispersion due to precipitation of the phosphor or the like is likely to occur, and when a liquid photosensitive resist is used as the slurry liquid, the dark reaction is accelerated. It has disadvantages such as poor storage stability. Furthermore, since printing methods such as screen printing are inferior in printing accuracy, there is a problem that it is difficult to cope with a larger PDP in the future.

To solve these problems, a method using a photosensitive element containing a phosphor (also referred to as a photosensitive film) has been proposed (JP-A-6-273925).
No.).

[0008] The method using a photosensitive element means that a photosensitive resin layer containing a phosphor of a photosensitive element comprising a photosensitive resin layer containing a phosphor and a support film is heat-pressed (laminated) to the PDP. Embedded in the space of the substrate for use, then, using a negative film, imagewise exposed to actinic light such as ultraviolet light by a photographic method, then, with a developing solution such as an aqueous alkaline solution, to remove the unexposed portions, Unnecessary organic components of the photosensitive resin layer containing the phosphor in the exposed portion are removed by baking, and a phosphor pattern is formed only in a necessary portion.

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

However, when the unexposed portion is removed with a developing solution, there is a problem that the phosphor surface is attacked and the luminance after firing is reduced.

[0011]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method of manufacturing a back plate for a plasma display panel which does not cause deterioration in phosphor luminance.

[0012]

That is, the present invention provides:
(I) a step of forming a phosphor-containing photosensitive resin composition layer on a plasma display panel substrate on which barrier ribs are formed; and (II) actinic light is applied to the phosphor-containing photosensitive resin composition layer. Image-irradiating step (III)
Forming a pattern by selectively removing unnecessary portions of the photosensitive resin composition layer containing the phosphor by development; and (I)
V) A method of manufacturing a back plate for a plasma display panel, which comprises a step of forming a phosphor pattern by removing unnecessary portions from the pattern by firing, wherein (III) developing a phosphor-containing photosensitive resin composition layer by development. In the step of selectively removing unnecessary portions to form a pattern, the contents of transition metal ions, sulfate ions, sulfite ions, nitrate ions, nitrite ions, chloride ions, and chlorine are each less than 500 ppm by weight. An object of the present invention is to provide a method for manufacturing a back plate for a plasma display panel, characterized by using a developer.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION

(I) In the step of forming a phosphor-containing photosensitive resin composition layer on a plasma display panel substrate on which barrier ribs are formed, the layer is formed by applying a phosphor-containing photosensitive resin composition Or using a photosensitive element having a layer of a photosensitive resin composition containing a phosphor. Examples of the photosensitive resin composition containing a phosphor include (a) a polymer binder, (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group at its terminal, and (c) free radicals upon irradiation with active light. And a mixture of a photoinitiator and (d) a phosphor.

(A) The polymer binder is preferably a vinyl copolymer. Examples of the vinyl monomer used in the vinyl copolymer include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid. , Methyl acrylate,
Methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, iso-propyl acrylate, i-methacrylate
So-propyl, n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-methacrylate Butyl, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, heptyl acrylate, heptyl methacrylate, 2-ethylhexyl acrylate, 2-methacrylic acid
Ethylhexyl, octyl acrylate, octyl methacrylate, nonyl acrylate, nonyl methacrylate, decyl acrylate, decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tetradecyl acrylate,
Tetradecyl methacrylate, hexadecyl acrylate,
Hexadecyl methacrylate, octadecyl acrylate,
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, methoxytriacrylate Ethylene glycol, methoxytriethylene glycol methacrylate 2-hydroxyethyl acrylate,
2-hydroxyethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate,
Diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate,
Dimethylaminopropyl methacrylate, acrylic acid 2-
Chloroethyl, 2-chloroethyl methacrylate, 2-fluoroethyl acrylate, 2-fluoroethyl methacrylate, 2-cyanoethyl acrylate, 2-methacrylic acid
Examples include cyanoethyl, styrene, α-methylstyrene, vinyl toluene, vinyl chloride, vinyl acetate, N-vinylpyrrolidone, butadiene, isoprene, chloroprene, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, and the like. These can be used alone or 2
Used in combination of more than one species.

(A) The weight average molecular weight of the polymer binder is
5,000 to 300,000, preferably 2
It is more preferable to be in the range of 0000 to 150,000. If the weight average molecular weight is less than 5,000, the film formability and flexibility of the photosensitive element tend to decrease, and if it exceeds 300,000, the developability (unnecessary portions are easily developed by development). Tend to be reduced).

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

Further, (a) the carboxyl group content (acid value (mgKOH / mgKOH / g) of the polymer binder is set so that the photosensitive resin composition containing the phosphor can be developed with a developer.
g) can be adjusted as appropriate.

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

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

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

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

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

(C) Examples of photoinitiators that generate free radicals upon irradiation with actinic light include aromatic ketones (benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-
Methoxy-4'-dimethylaminobenzophenone, 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 (methyl benzoin, ethyl benzoin, etc.), benzyl derivative (2-benzyl-2) -Dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,2-dimethoxy-1,2-diphenylethan-1-one, benzyldimethylketal, etc.), 2,4,5-triarylimidazole Monomer (2- (o-chlorophenyl) -4,5-
Diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-
Diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2
-(P-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl)
-5-phenylimidazole dimer, 2- (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.

(D) The phosphor is not particularly limited.
Those mainly composed of ordinary metal oxides can be used.

As a red-colored phosphor, for example, Y ₂
O ₂ S: Eu, Zn ₃ (PO ₄ ) ₂ : Mn, Y ₂ O ₃ : Eu,
YVO ₄ : Eu, (Y, Gd) BO ₃ : Eu, γ-Zn ₃
(PO ₄ ) ₂ : Mn, (ZnCd) S: Ag + In ₂ O and the like.

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

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

The amount of component (a) is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, based on 100 parts by weight of the total of components (a) and (b). preferable. When the blending amount is less than 10 parts by weight, the photocured product tends to become brittle, and when supplied in the form of a roll as a photosensitive element to be described later, the phosphor-containing photosensitive resin composition has a roll end portion. Extrusion (hereinafter referred to as edge fusion) makes it difficult to feed out the photosensitive element from a roll during lamination, or the extruded portion is partially and excessively embedded in the space of the PDP substrate, resulting in a manufacturing yield. In particular, there is a tendency that the film-forming property is remarkably reduced, and the film-forming property is lowered. When the content exceeds 90 parts by weight, the sensitivity tends to be insufficient.

The amount of component (b) is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, based on 100 parts by weight of the total of components (a) and (b). preferable. If the amount is less than 10 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, In the case of a photosensitive element, the photosensitive resin composition containing the phosphor tends to exude from the end due to the flow, and the film-forming property tends to be reduced.

The amount of the component (c) is 0.01 to 3 parts by weight based on 100 parts by weight of the total of the components (a) and (b).
It is preferably 0 parts by weight, more preferably 0.1 to 20 parts by weight. When the amount is less than 0.01 part by weight, the sensitivity of the phosphor-containing photosensitive resin composition tends to be insufficient, and when the amount exceeds 30 parts by weight,
The absorption of active light on the exposed surface of the photosensitive resin composition containing the phosphor tends to increase, and the internal light curing tends to be insufficient.

The amount of the component (d) is as follows:
The amount is preferably from 10 to 400 parts by weight, and more preferably from 50 to 400 parts by weight, based on 100 parts by weight of the total of the components (b) and (c).
More preferably 380 parts by weight, and 70 to 350 parts by weight.
It is particularly preferred to use parts by weight. This blending amount is 10
If the amount is less than parts by weight, the luminous efficiency tends to decrease when light is emitted as a PDP, and if it exceeds 400 parts by weight, the film formability or flexibility decreases when the photosensitive element is used. Tend.

The phosphor-containing photosensitive resin composition of the present invention may contain a compound having a carboxyl group 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,
Examples thereof include aromatic dibasic acids, aliphatic tribasic acids, and aromatic tribasic acids.

Specifically, for example, formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, propionic acid,
Capric, undecanoic, lauric, tridecanoic, myristic, pentadecanoic, palmitic, heptadecanoic, stearic, nonadecanoic, arachidic, palmitooleic, oleic, elaidic, linolenic, linoleic, Oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, monomethyl malonate,
Monoethyl malonate, succinic acid, methylsuccinic acid, adipic acid, methyladipic acid, pimelic acid, suberic acid,
Azelaic acid, sebacic acid, maleic acid, itaconic acid,
Examples include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, citric acid, salicylic acid, pyruvic acid, malic acid and the like. Among them, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, citric acid and the like are preferable, and oxalic acid, malonic acid, citric acid and the like are more preferable 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 10 parts by weight, the effect of storage stability tends to decrease, and if it exceeds 30 parts by weight, sensitivity tends to be insufficient.

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

As dispersants, inorganic dispersants (silica gel, bentonite, kaolinite, talc, hectorite, montmorillonite, saponite, beidellite, etc.) and organic dispersants (aliphatic amide, fatty Group-based esters, polyethylene oxides, sulfate ester-based anionic surfactants, polycarboxylic acid amine salts, polycarboxylic acids, polyamides, polymer polyethers, acrylic copolymers, special silicones, etc.) Can be
These can be used alone or in combination of two or more.

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

In the present invention, it is preferable to use a binder in the photosensitive resin composition containing a phosphor in order to prevent the phosphor from peeling off the PDP substrate after firing. 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.
The amount is preferably 0.01 to 100 parts by weight, more preferably 0.05 to 50 parts by weight, and particularly preferably 0.1 to 30 parts by weight based on 100 parts by weight of the component. 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.

A plasticizer can be added to the phosphor-containing photosensitive resin composition of the present invention in order to improve the film properties when the composition is used as a photosensitive element.

The plasticizer is represented by the general formula (I)

[0042]

Embedded image (Wherein, R represents a hydrogen atom or a methyl group, Y ¹ represents a hydrogen atom or a saturated hydrocarbon group or a polyalkylene glycol residue which may have a substituent, and Y ² represents
A hydroxyl group or a saturated hydrocarbon group or a polyalkylene glycol residue which may have a substituent;
Alkylene glycol derivatives such as polypropylene glycol and its derivatives, polyethylene glycol and its derivatives, and dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, and biphenyl diphenyl. Phosphate and the like.

The amount of the plasticizer is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, based on 100 parts by weight of the component (a).
It is particularly preferred that the amount be 30 to 70 parts by weight. If the compounding amount is less than 10 parts by weight, when the photosensitive element is used, there is a tendency that the film formability is reduced and the like.
When the amount is more than the weight part, the sensitivity of the photosensitive resin composition containing photosensitive tends to be insufficient.

The photosensitive resin composition containing a phosphor used 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 or the like can be added as needed.

The photosensitive element used in the present invention comprises:
It has a photosensitive resin composition layer containing the phosphor on a support film.

The support film of the photosensitive resin composition layer containing the phosphor of the photosensitive element may be a chemically and thermally stable and flexible material, for example, polyethylene. Terephthalate, polycarbonate, polyethylene, polypropylene and the like,
Among them, polyethylene terephthalate and polyethylene are preferred, and polyethylene terephthalate is more preferred. The thickness of the support film is preferably 5 to 100 μm, more preferably 10 to 80 μm.

The photosensitive element is a uniformly dispersed solution obtained by dissolving or mixing the components constituting the photosensitive resin composition layer containing the phosphor in a solvent capable of dissolving or dispersing. Can be obtained by coating and drying on a support film.

Examples of the solvent capable of dissolving or dispersing the above components constituting the photosensitive resin composition containing the phosphor used in 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.

Examples of the coating method include a doctor blade coating method, a miller bar coating method, a roll coating method, a screen coating method, a spinner coating method, an ink jet coating method, a spray coating method, a dip coating method, a gravure coating method, and a curtain coating method. Method or the like can be used.

As the drying method, drying can be performed by using a known drying method. The drying temperature is preferably 60 to 130 ° C., and the drying time is preferably 3 minutes to 1 hour.

The thickness of the photosensitive resin composition layer having the phosphor of the photosensitive element is not particularly limited, but may be from 10 to 20.
The thickness is preferably 0 μm, more preferably 20 to 100 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 decreases. As a result, the luminous efficiency tends to decrease.

The phosphor-containing photosensitive resin composition used in the present invention has a viscosity at 100 ° C. of 1 to 1 × 10 ^9.
Pa · sec, preferably 2 to 1 × 10 ⁸ P
a · sec, more preferably 5 to 1 × 10 ⁷
Pa · sec is particularly preferable, and 10 to 1 × 1
It is extremely preferable to set the pressure at 0 ⁶ Pa · sec. This one
If the viscosity at 00 ° C. is less than 1 Pa · sec, the viscosity at room temperature becomes too low, and when the photosensitive element is used, the photosensitive resin composition layer containing the phosphor tends to exude from the edge due to flow. And the film-forming properties tend to decrease. On the other hand, if it exceeds 1 × 10 ⁹ Pa · sec, the formability of the photosensitive resin composition layer containing the phosphor on the inner surface of the concave portion of the substrate having irregularities described later tends to decrease.

A peelable cover film can be further laminated on the photosensitive resin composition layer containing the phosphor of the photosensitive element. Examples of the cover film include polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, and the like. The adhesive strength between the support film and the photosensitive resin composition layer containing the phosphor is higher than that of the cover film and the photosensitive resin containing the phosphor. It is preferable that the adhesive strength with the resin composition layer is smaller. The photosensitive element thus obtained is
It can be stored in a roll.

Further, the photosensitive element may have a thermoplastic resin layer on a support film and a photosensitive resin composition layer containing a phosphor thereon. Here, as the support film, the same as the support film used for the photosensitive element having the photosensitive resin composition layer containing the phosphor described above can be used.

The resin constituting the thermoplastic resin layer is not particularly limited as long as it can be softened at the temperature at the time of thermocompression bonding. Examples thereof include polyethylene, polypropylene, polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride, and the like. Polystyrene, polyvinyl toluene, polyacrylate, polymethacrylate, copolymer of ethylene and vinyl acetate, copolymer of ethylene and acrylate, copolymer of vinyl chloride and vinyl acetate, styrene and acrylate Or a copolymer of methacrylic acid ester, a copolymer of vinyl toluene and an acrylic acid ester or a methacrylic acid ester, a polyvinyl alcohol-based resin (a hydrolyzate of a polyacrylic acid ester or a polymethacrylic acid ester, Decomposition products, ethylene and vinyl acetate With a hydrolyzate of a copolymer with, a hydrolyzate of a copolymer of ethylene and an acrylate, a hydrolyzate of a copolymer of vinyl chloride and vinyl acetate, styrene and an acrylate or methacrylate, Hydrolysates of copolymers of the following, hydrolysates of copolymers of vinyl toluene and acrylic or methacrylic esters, etc.), water-soluble salts of carboxyalkylcellulose, water-soluble cellulose ethers, and water-soluble carboxyalkyl starch. And a carboxyl group-containing resin obtained by copolymerizing a neutral salt, polyvinylpyrrolidone, an unsaturated carboxylic acid and an unsaturated monomer copolymerizable therewith.

The thermoplastic resin layer may be one in which the thermoplastic resin layer and the photosensitive resin composition layer containing the phosphor can be developed using the same developer in a developing step described later. This is preferable because the number of steps can be reduced.

The following can be developed with the same developer:
Examples thereof include those soluble in water or an aqueous alkali solution.

Examples of the resin constituting the thermoplastic resin layer soluble in water or an aqueous alkali solution include polyvinyl alcohol resins (a hydrolyzate of a polyacrylic ester or a polymethacrylic ester, a hydrolyzate of a polyvinyl acetate). , A hydrolyzate of a copolymer of ethylene and vinyl acetate, a hydrolyzate of a copolymer of ethylene and acrylate, a hydrolyzate of a copolymer of vinyl chloride and vinyl acetate, styrene and acrylate Or a hydrolyzate of a copolymer with methacrylic acid ester, a hydrolyzate of a copolymer of vinyl toluene with an acrylic acid ester or a methacrylic acid ester, etc.), a water-soluble salt of carboxyalkyl cellulose, a water-soluble cellulose ether, Water-soluble salts of carboxyalkyl starch, polyvinylpyrrolidone, unsaturated carboxylic acids A resin having a carboxyl group obtained by copolymerizing et copolymerizable unsaturated monomers.

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.), methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, iso-propyl acrylate, iso-propyl methacrylate, N-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, iso-methacrylate
Butyl, sec-butyl acrylate, methacrylic acid sec
c-butyl, tert-butyl acrylate, tert-butyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, heptyl acrylate, heptyl methacrylate, 2-ethylhexyl acrylate, 2-methacrylic acid Ethylhexyl, octyl acrylate, octyl methacrylate,
Nonyl acrylate, nonyl methacrylate, decyl acrylate, decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, acrylic acid Eicosyl, eicosyl methacrylate, docosyl acrylate, docosyl methacrylate, cyclopentyl acrylate, cyclopentyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, cycloheptyl acrylate, cycloheptyl methacrylate, benzyl acrylate, benzyl methacrylate, acrylic acid Phenyl, phenyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, acrylic acid Toxiethylene glycol, methoxydiethylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, Dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, 2-chloroethyl acrylate, 2-chloroethyl methacrylate, acrylic acid 2
-Fluoroethyl, 2-fluoroethyl methacrylate,
2-cyanoethyl acrylate, 2-cyanoethyl methacrylate, styrene, α-methylstyrene, vinyltoluene, vinyl chloride, vinyl acetate, N-vinylpyrrolidone,
It is preferable to use a vinyl copolymer obtained by copolymerizing a vinyl monomer such as butadiene, isoprene, chloroprene, acrylamide, methacrylamide, acrylonitrile, and methacrylonitrile.

The resin having a carboxyl group obtained by copolymerizing an unsaturated carboxylic acid and an unsaturated monomer copolymerizable therewith has a weight average molecular weight of 5,000.
~ 300,000, preferably 20,000
More preferably, it is set to １５０150,000. If the weight average molecular weight is less than 5,000, the film formability and flexibility of the photosensitive element tend to decrease, and if it exceeds 300,000, the developability (unnecessary portions are easily developed by development). Tend to be reduced). The weight average molecular weight is a value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve.

Further, a thermoplastic resin layer soluble in an aqueous alkali solution is obtained by copolymerizing an unsaturated carboxylic acid and an unsaturated monomer copolymerizable therewith so as to be developable with a developer. The carboxyl group content (which can be defined by an acid value (mgKOH / g)) of the resulting resin having a carboxyl group can be appropriately adjusted.

For example, when developing using an aqueous alkali solution such as sodium carbonate and potassium carbonate, the acid value is adjusted to 9
It is preferable to set it 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.

When developing using an aqueous developing solution 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 2
If it exceeds 60, the developer resistance tends to decrease.

In order to improve the film properties of the thermoplastic resin layer, a plasticizer may be added to the resin constituting the thermoplastic resin layer.

As the plasticizer, all of the plasticizers usable in the photosensitive resin composition constituting the photosensitive resin composition layer containing the phosphor can be used.

The amount of the plasticizer is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, based on 100 parts by weight of the total resin constituting the thermoplastic resin layer. It is particularly preferred that the amount be from 70 to 70 parts by weight. If the compounding amount is less than 10 parts by weight, the film forming property tends to be reduced when the photosensitive element is used, and if it exceeds 90 parts by weight, the thermoplastic resin layer is used when the photosensitive element is used. Tend to exude from the edge due to flow.

Also, in the photosensitive resin composition constituting the photosensitive resin composition layer containing the phosphor, (b) migration of a photoinitiator which generates free radicals upon irradiation with active light to the thermoplastic resin layer. (B) free radicals are generated by irradiation of active light in the photosensitive resin composition constituting the photosensitive resin composition layer containing the phosphor in the resin constituting the thermoplastic resin layer in order to prevent the occurrence of The same kind as the photoinitiator,
A photoinitiator that generates free radicals upon irradiation with the same amount of active light can also be added.

As a method for providing a thermoplastic resin layer on a support film in the present invention, a uniform solution is obtained by dissolving or mixing the resin constituting the thermoplastic resin layer in a solvent that dissolves the resin. It can be formed on a support film by coating and drying using a known coating method such as a knife coating method, a roll coating method, a spray coating method, a gravure coating method, a bar coating method, a curtain coating method, and the like. .

Examples of the solvent for dissolving the resin constituting the thermoplastic resin layer include water, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, γ-butyrolactone, N-
Methylpyrrolidone, dimethylformamide, tetramethylsulfone, diethylene glycol dimethyl ether,
Examples thereof include diethylene glycol monobutyl ether, chloroform, methylene chloride, methyl alcohol, and ethyl alcohol. These are used alone or in combination of two or more.

The thickness of the thermoplastic resin layer is not particularly limited.
２００200 μm, preferably 20-100 μm
Is more preferable.

A photosensitive element having a thermoplastic resin layer on a support film and a photosensitive resin composition layer containing a phosphor on the thermoplastic resin layer can be obtained by adding a photosensitive resin composition layer containing a phosphor to the photosensitive element. It can be obtained by dissolving or mixing each of the constituent components in a solvent capable of dissolving or dispersing to form a uniformly dispersed solution, applying the solution on the thermoplastic resin layer provided above, and drying.

The components constituting the photosensitive resin composition layer containing the phosphor are dissolved or mixed in a solvent capable of dissolving or dispersing to form a uniformly dispersed solution, and the thermoplastic resin provided above is provided. The method of coating and drying on the layer can be the same method as the method of obtaining a photosensitive element having a photosensitive resin composition layer containing a phosphor on a support film.

The thickness of the photosensitive resin composition layer containing the phosphor of the photosensitive element is not particularly limited.
It is preferably set to 00 μm, and more preferably set to 20 to 80 μm. 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 the thickness exceeds 100 μm, the phosphor pattern after firing tends to be thick and the luminous area of the phosphor screen tends to decrease and the luminous efficiency tends to decrease. is there.

On the photosensitive resin composition layer containing the phosphor of the photosensitive element, a peelable cover film can be further laminated.

As the cover film, polyethylene,
Polypropylene, polyethylene terephthalate, polycarbonate and the like, and the adhesive force between the cover film and the photosensitive resin composition layer containing the phosphor is smaller than the adhesive force between the support film and the thermoplastic resin layer. Preferably, there is.

The photosensitive element is formed into a uniform solution by dissolving or mixing each of the components constituting the photosensitive resin composition layer containing the phosphor in the solvent capable of dissolving or dispersing. The phosphor is contained by coating and drying on the support film using a known coating method such as a knife coating method, a roll coating method, a spray coating method, a gravure coating method, a bar coating method, and a curtain coating method. After the photosensitive resin composition layer is formed, the photosensitive resin composition layer containing the phosphor and the thermoplastic resin layer provided on the support film may be bonded to each other so as to be in contact with each other. The photosensitive element thus obtained can be stored in a roll.

Hereinafter, each step of the method for manufacturing the back plate for a plasma display panel of the present invention will be described in detail. FIGS. 3 and 4 are schematic views showing each step of the method for forming a phosphor pattern in the present invention.

[(I) Step of Forming (A) Photosensitive Resin Composition Layer Containing Phosphor on Plasma Display Panel Substrate with Barrier Rib Formed] On PDP Substrate 1 with Barrier Rib 2 Formed FIG. 3 shows a state in which the photosensitive resin composition layer 5 containing the phosphor (A) is formed.
(III).

As the PDP substrate 1 in the present invention,
For example, a substrate in which electrodes and barrier ribs are formed on a substrate such as a glass plate or a synthetic resin, which may be subjected to a surface treatment for transparent bonding, may be used. For forming the barrier rib, a known material can be used without any particular limitation. For example, a rib material containing silica, a thermosetting resin, a low-melting glass (such as lead oxide), a solvent, or the like can be used.

Further, in addition to the electrodes and barrier ribs, a dielectric film, an insulating film, an auxiliary electrode, a resistor, and the like may be formed on the PDP substrate, if necessary.

The method for forming these on a substrate is not particularly limited. For example, electrodes can be formed on a substrate by a method such as vapor deposition, sputtering, plating, coating, printing, and the like. Barrier ribs can be formed by a method such as sandblasting or embedding. The barrier rib usually has a height of 20 to 500 μm and a width of 20 to 20 μm.
0 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, a triangular shape, an elliptical shape, etc., and is usually shown in FIGS. Thus, a grid-like or stripe-like discharge space is formed.

In FIGS. 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. In the case of a grid-like discharge space as shown in FIG. 1, the vertical and horizontal lengths are 50 μm to 1 mm.
In a striped discharge space as shown in FIG.
m to 1 mm.

In FIG. 3 (III), a method of forming (A) the photosensitive resin composition layer 5 containing the phosphor on the PDP substrate 1 on which the barrier ribs 2 are formed is as follows.
For example, it can be obtained by dissolving or mixing the above-mentioned components in a solvent capable of dissolving or dispersing to form a uniformly dispersed solution, and then applying and drying the solution on the PDP substrate.

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

Examples of the coating method include doctor blade coating, miller bar coating, roll coating, screen coating, spinner coating, inkjet coating, spray coating, dip coating, gravure coating, and curtain coating. Method or the like can be used.

As a drying method, drying can be performed by using a known drying method, and the drying temperature is 40 to 130 ° C.
The drying time is preferably 10 to 90 minutes.

In FIG. 3 (III), as a method of forming (A) the photosensitive resin composition layer 5 containing the phosphor on the PDP substrate 1 on which the barrier ribs 2 are formed, for example, It can also be obtained by a method using a sex element.

The method of using the photosensitive element means that the photosensitive element (A) is coated on the photosensitive resin composition layer containing the phosphor, and In a state where the plastic resin layer is arranged, a method of heating and pressing from above the layer (B) can be used.

When a photosensitive element is used, if a cover film is present on the photosensitive element, after removing the cover film, the photosensitive element (A) The photosensitive resin composition layer 5 containing the phosphor may be simply placed so as to be in contact therewith, may be pressurized by a pressure roll or the like, or may be laminated under reduced pressure. FIG. 3I shows a state in which the photosensitive element (A) of the photosensitive element and the photosensitive resin composition layer 5 containing the phosphor are laminated on the PDP substrate 1 on which the barrier ribs 2 are formed.

[0091] The pressure for pressurization is 50 to 50 in linear pressure.
It is preferably 1 × 10 ⁵ N / m, and 2.5 × 10 ²
-5 × 10 ⁴ N / m, more preferably 5 × 1 ⁴ N / m.
It is particularly preferred to be in the range of 0 ² to 4 × 10 ⁴ N / m. If the pressure is less than 50 N / m, the embedding property of (A) the photosensitive resin composition layer 5 containing the phosphor into the space of the PDP substrate tends to decrease, and 1 × 10 ⁵ N / m is required. If it exceeds, the barrier rib of the PDP substrate tends to be broken.

In order to further improve the embedding property of the photosensitive resin composition layer 5 containing the phosphor (A) into the space, the surface of the pressure roll is rich in rubber and plastic. A material of a material can also be used.
The thickness of the layer made of a material having a high flexibility is 200 to 40.
Preferably, it is 0 μm.

(A) In order to further improve the embedding property of the photosensitive resin composition layer 5 containing the phosphor into the space, the barrier rib of the PDP substrate is heated while heating the photosensitive element with a heating roll or the like. It can also be laminated by pressing on the surface on which is formed.

The heating temperature during thermocompression bonding is 10 to 130 ° C.
The temperature is preferably set to 20 to 120 ° C, more preferably 30 to 110 ° C. If the heating temperature is lower than 10 ° C., the photosensitive resin composition layer 5 containing the phosphor (A) tends to be unable to sufficiently adhere to the PDP substrate.
(A) The photosensitive resin composition layer 5 containing the phosphor tends to be thermally cured.

Further, the pressing pressure at the time of heating and pressing is a linear pressure of 5
0 to 1 × 10 ⁵ N / m, preferably 2.5 ×
It is more preferably 10 ^{2 to} 5 × 10 ⁴ N / m, and 5
It is particularly preferable to set it to × 10 ² to 4 × 10 ⁴ N / m.
If the pressure is less than 50 N / m, the embedding property of (A) the photosensitive resin composition layer 5 containing the phosphor into the space of the PDP substrate tends to decrease, and 1 × 10 ⁵ N / m is required. If it exceeds, the barrier rib of the PDP substrate tends to be broken.

If the photosensitive element is heated as described above, it is not necessary to preheat the PDP substrate on which the barrier ribs have been formed, but (A) the space in the photosensitive resin composition layer 5 containing the phosphor is required. In order to further improve the embedding property in the PDP, it is preferable to perform a pre-heat treatment on the PDP substrate.

Further, for the same purpose, the above-mentioned compression bonding and heating compression bonding can be performed under reduced pressure of 5 × 10 ⁴ Pa or less.

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

(A) A thermoplastic resin layer 6 (B) is disposed on a photosensitive resin composition layer 5 containing a phosphor, and (A) a photosensitive resin composition containing a phosphor FIG. 3 (II) shows a state in which the material layer 5 and the (B) thermoplastic resin layer 6 are laminated.

In FIG. 3 (II), a method of (A) disposing a thermoplastic resin layer 6 above a phosphor-containing photosensitive resin composition layer 5 and heating and pressing the same is as follows. If a support film is present on the (A) phosphor-containing photosensitive resin composition layer 5 in the state of FIG. 3 (I), after removing the support film, the (A) fluorescence A (B) thermoplastic resin layer 6 (after the cover film is present, after removing the cover film) is disposed on the photosensitive resin composition layer 5 containing the body, and a heating roll 7 is provided.
And the like, and a method of thermocompression bonding.

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 less than 10 ° C., the embedding property of the (A) photosensitive resin composition layer 5 containing the phosphor into the space of the PDP substrate tends to decrease. If the heating temperature exceeds 130 ° C., (A) The photosensitive resin composition layer 5 containing the phosphor tends to be thermally cured.

Further, the pressing pressure at the time of heating and pressing is a linear pressure of 5
0-1 × 10^FiveN / m, preferably 2.5 × 1
0^Two~ 5 × 10^FourN / m, more preferably 5 ×
10 ^Two~ 4 × 10^FourN / m is particularly preferred. This
If the compression pressure is less than 50 N / m, (A)
Of the photosensitive resin composition layer 5 having the PDP substrate in the space
1 × 10^FiveOver N / m
The barrier ribs of the PDP substrate tend to be destroyed
is there.

(B) If the thermoplastic resin layer 6 is heated as described above, it is not necessary to preheat the PDP substrate on which the photosensitive resin composition layer 5 containing the phosphor (A) is laminated. However, from the viewpoint of further improving the embedding property of the photosensitive resin composition layer 5 containing the phosphor in the space (A),
(A) It is preferable that the PDP substrate on which the photosensitive resin composition layer 5 containing the phosphor is laminated is preheat-treated. The preheating temperature at this time is preferably 30 to 130 ° C., and the preheating time is preferably 0.5 to 20 minutes.

Further, from the viewpoint of further improving the embedding property of the photosensitive resin composition layer 5 containing the phosphor (A) into the space, the surface of the pressure roll is rich in flexibility such as rubber and plastic. A material of a material can also be used.
The thickness of the layer made of a material having a high flexibility is 200 to 40.
Preferably, it is 0 μm.

Further, for the same purpose, the above-mentioned press-bonding and heat-pressing operations can be performed under a reduced pressure of 5 × 10 ⁴ Pa or less.

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

In this manner, (A) the photosensitive resin composition layer 5 containing the phosphor can be uniformly formed in the space of the PDP substrate.

Further, in the step (I) in the present invention,
(A) Photosensitive resin composition layer 5 containing phosphor and (B)
It is also possible to laminate two thermoplastic resin layers 6 while simultaneously thermocompression bonding. The thermocompression bonding conditions for simultaneous thermocompression bonding of two layers are as described in (B) Thermoplastic resin layer 6 above.
Can be used when heat-pressing.

The method of laminating (A) the photosensitive resin composition layer 5 containing the phosphor on the PDP substrate 1 on which the barrier ribs 2 are formed is, for example, as follows. ) Having a thermoplastic resin layer, on which
(A) It can also be obtained by a method using a photosensitive element having a photosensitive resin composition layer containing a phosphor.

On a substrate for a plasma display panel (substrate for PDP) 1 on which a barrier rib 2 is formed, a book including (B) a thermoplastic resin layer 6 and (A) a photosensitive resin composition layer 5 containing a phosphor is provided. FIG. 4 shows a state in which the photosensitive elements of the present invention are laminated using the heating roll 7.

In the steps of FIGS. 4 (II) and (III),
The method for laminating the photosensitive element of the present invention including the (B) thermoplastic resin layer 6 and the (A) photosensitive resin composition layer 5 containing a phosphor on the PDP substrate 1 on which the barrier ribs 2 are formed is as follows. For example, when a cover film is present on the photosensitive element, after removing the cover film, the surface of the PDP substrate on which the barrier ribs are formed,
(A) The layers can be laminated by, for example, heat-pressing with a heating roll 7 so that the photosensitive resin composition layer 5 containing the phosphor is in contact with the layer.

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 less than 10 ° C., the embedding property of the (A) photosensitive resin composition layer 5 containing the phosphor into the space of the PDP substrate tends to decrease. If the heating temperature exceeds 130 ° C., (A) The photosensitive resin composition layer 5 containing the phosphor tends to be thermally cured.

[0113] The compression pressure during the heat compression bonding is 5 linear pressure.
0-1 × 10^FiveN / m, preferably 2.5 × 1
0^Two~ 5 × 10^FourN / m, more preferably 5 ×
10 ^Two~ 4 × 10^FourN / m is particularly preferred. This
If the compression pressure is less than 50 N / m, (A)
Of the photosensitive resin composition layer 5 having the PDP substrate in the space
1 × 10^FiveOver N / m
The barrier ribs of the PDP substrate tend to be destroyed
is there.

When the photosensitive element of the present invention including the (B) thermoplastic resin layer 6 and the (A) phosphor-containing photosensitive resin composition layer 5 is heated as described above, the PDP substrate is pre-heated. Although it is not necessary, it is preferable that the PDP substrate be pre-heated from the viewpoint of further improving the embeddability of the (A) photosensitive resin composition layer 5 containing the phosphor in the space. The preheating temperature at this time is preferably 30 to 130 ° C., and the preheating time is preferably 0.5 to 20 minutes.

Further, from the viewpoint of further improving the embedding property of the photosensitive resin composition layer 5 containing the phosphor (A) into the space, the surface of the pressure roll is rich in flexibility such as rubber and plastic. A material of a material can also be used.
The thickness of the layer made of a material having a high flexibility is 200 to 40.
Preferably, it is 0 μm.

Further, for the same purpose, the above-mentioned press-bonding and heat-pressing operations can be performed under reduced pressure of 5 × 10 ⁴ PA or less.

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

Thus, (A) the photosensitive resin composition layer 5 containing the phosphor can be uniformly formed in the space of the PDP substrate.

Further, the heating conditions, pressure conditions, and preheating conditions of the PDP substrate described above during the thermocompression bonding, (B)
By changing the combination of the conditions such as the thickness of the thermoplastic resin layer 6, the layers can be laminated as shown in FIG. FIG. 5 is an example after the step (I) in the method for producing a phosphor pattern of the present invention.

During the production of the PDP substrate before the photosensitive elements are laminated, heating may cause the PDP substrate to shrink entirely or partially, or may cause the PDP substrate to hardly shrink. When the whole or partial shrinkage of the PDP substrate occurs,
From the viewpoint of increasing the margin of positioning accuracy in the step of (II) imagewise irradiating actinic rays described below, FIG.
As shown in (IV), it is preferable that the photosensitive resin composition layer 5 is laminated on the inner surface of the concave portion so that the photosensitive resin composition layer 5 hardly remains on the upper portion of the convex portion. As shown in FIG. 5, the photosensitive resin composition layer 5 may be laminated in a state where the photosensitive resin composition layer 5 remains on the convex portions.

[(II) Step of irradiating the photosensitive resin composition layer containing the phosphor imagewise with actinic rays] The state of irradiating actinic rays 9 imagewise is shown in FIG. 3 (IV). FIG. 3 (I
In the step (V), the actinic rays 9 may be radiated imagewise as (B) above the thermoplastic resin layer 6 in a state shown in FIG. 3 (III) through a photomask 8 such as a negative film or a positive film. Thus, the actinic ray 7 can be irradiated imagewise. At this time, if a support film is present on the thermoplastic resin layer (B), the active film 9 may be irradiated imagewise while the support film is being laminated. After the removal, the actinic rays 9 may be irradiated imagewise.

At this time, (B) the thermoplastic resin layer 6
Is the photosensitive resin composition described above, (B)
The thermoplastic resin layer 6 and the photosensitive resin composition layer 5 containing the phosphor (A) are simultaneously photo-cured.

Further, (A) water, an alkaline aqueous solution, a semi-solvent aqueous solution, a semi-solvent alkaline aqueous solution, an organic solvent or the like which does not dissolve the photosensitive resin composition layer 5 containing the phosphor is used.
(B) After removing the thermoplastic resin layer 6 by dissolution, the actinic ray 9 can be imagewise irradiated through a photomask 8 such as a negative film or a positive film.

As the actinic ray 9, a known actinic light source can be used, and examples thereof include light generated from a carbon arc, a mercury vapor arc, a xenon arc, and others.

Since the sensitivity of the photoinitiator is usually maximum 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 9 and the light source is as described above. Other than the above, a flood light bulb for photography, a sun lamp and the like can be used.

[(III) Step of selectively removing unnecessary portions of photosensitive resin composition layer containing a phosphor by development to form a pattern] FIG. 3 (V) shows a state where the unnecessary portions are removed by development. It was shown to. In FIG. 3 (V), 5 '
Is a photosensitive resin composition layer containing a phosphor after photocuring.

In the step of FIG. 3 (V), for example, as a developing method, after the state of FIG. 3 (IV), (B) when a support film exists on the thermoplastic resin layer 6,
After removing this, using a known developing solution such as an alkaline aqueous solution, an aqueous developing solution, and an organic solvent, spraying, rocking immersion,
A method in which development is performed by a known method such as brushing or scrubbing to remove unnecessary portions, and the like can be given. In the present invention, in the step (III) of removing unnecessary portions by development, the contents of transition metal ions, sulfate ions, sulfite ions, nitrate ions, nitrite ions, chloride ions and chlorine are each less than 500 ppm by weight, It is characterized in that a developer having preferably less than 200 ppm is used. The total amount of these ions and chlorine is preferably less than 2000 ppm, more preferably 500 p.
Desirably less than pm. Such a developer is
For example, it can be obtained by using ion-exchanged water.

When removing unnecessary portions, first, (A)
(B) The thermoplastic resin layer 6 is removed by dissolution using water, an alkaline aqueous solution, an aqueous developer, an organic solvent or the like which does not dissolve the phosphor-containing photosensitive resin composition layer 5, and then the developer is used. (A) The unnecessary portion of the photosensitive resin composition layer 5 containing the phosphor may be removed.
The thermoplastic resin layer 6 is the same as the (B) thermoplastic resin layer 6 described above.
And (A) the photosensitive resin composition layer 5 containing the phosphor,
When the same developer can be used for development, the developer can be used for (B) thermoplastic resin composition layer 6
And (A) the unnecessary portion of the photosensitive resin composition 5 containing the phosphor can be removed in one step.

Also, (B) the thermoplastic resin layer 6 and (A)
As a method of removing unnecessary portions of the photosensitive resin composition layer 5 containing a phosphor, dry development can be performed individually or in one step.

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

The pH of the alkaline aqueous solution used for the developer is
Preferably, the temperature is 9 to 11, and the temperature is
It can be adjusted according to the developability of (B) the thermoplastic resin layer 6 and (A) the photosensitive resin composition layer 5 containing the phosphor.

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

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 aqueous alkali solution,
Other than the above substances, for example, borax, sodium metasilicate, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,
3-propanediol, 1,3-diaminopropanol-2-morpholine, tetramethylammonium hydroxide and the like.

The pH of the aqueous developer is preferably from 8 to 12, more preferably from 9 to 10.

Examples of the organic solvent include acetone alcohol, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether. Butyl ether and the like. These are used alone or in combination of two or more. 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.

Further, 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. Water may be added to these organic solvents in the range of 1 to 20% by weight to prevent ignition.

For the purpose of preventing the deterioration of the developing solution and the phosphor, the photosensitive resin composition layer 5 'containing the phosphor after photocuring and the (B) thermoplastic resin layer 6 are made of the above-mentioned photosensitive resin. In the case of a water-soluble resin composition, the base of the aqueous alkali solution remaining in the thermoplastic resin layer after photocuring, using an organic acid or an inorganic acid or an aqueous solution of these acids, spraying, induction immersion,
Acid treatment (neutralization treatment) can be performed by a known method such as brushing or scrapping.

Examples of the acid include organic acids and inorganic acids such as saturated fatty acids, unsaturated fatty acids, aliphatic dibasic acids, aromatic dibasic acids, aliphatic tribasic acids, and aromatic tribasic acids.

Specific organic acids include, for example, formic acid,
Acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, propionic acid, capric acid, undecanoic acid, lauric acid,
Tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, palmito oleic acid, oleic acid,
Elaidic acid, linolenic acid, linoleic acid, oxalic acid, malonic acid, methyl malonic acid, ethyl malonic acid, monomethyl malonate, monoethyl malonate, succinic acid, methyl succinic acid, adipic acid, methyl adipic acid, pimelic acid, suberic acid , Azelaic acid, sebacic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, citric acid, salicylic acid, pyruvic acid, malic acid and the like.

Further, specific inorganic acids include, for example,
Sulfuric acid, hydrochloric acid, nitric acid and the like. The pH of the aqueous acid solution used for the acid treatment is preferably 2 to 6, but the pH and temperature of the aqueous acid solution are determined by adjusting the pH of the photosensitive resin composition layer 5 ′ containing the phosphor after photocuring and the PDP substrate. It can be adjusted according to acid resistance (durability that does not deteriorate with acid).

After the development, UV irradiation or heating using a high-pressure mercury lamp or the like may 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 may be accompanied by heating. Further, the temperature at the time of heating is preferably from 60 to 180 ° C.,
More preferably, the temperature is set to 80 ° C. The heating time is
It is preferably 15 to 90 minutes.

Irradiation and heating of these ultraviolet rays may be performed separately from irradiation and heating, or either one may be performed first.

[(IV) Step of Removing Unwanted Parts from the Pattern by Firing to Form Phosphor Pattern] FIG. 3 (VI) shows a state in which the phosphor pattern has been formed after the unnecessary portions have been removed by firing. Was. In FIG. 3 (VI), reference numeral 10 denotes a phosphor pattern.

In the step of FIG. 3 (VI), the firing method is not particularly limited, and a known firing method is used to remove unnecessary substances other than the phosphor and the binder to form a phosphor pattern. be able to.

The firing temperature at this time is 350 to 800 ° C.
And more preferably 400 to 600 ° C. The firing time is preferably from 3 to 120 minutes, more preferably from 5 to 90 minutes.

The method for producing a phosphor pattern according to the present invention is characterized in that (I) according to the present invention is advantageous in that the number of steps can be reduced.
After repeating the steps (III) to (III) for each color to form a multicolor pattern composed of a photosensitive tree composition containing a phosphor that emits red, green, and blue, the step (IV) is performed. It is preferable to form a multicolor pattern.

In the present invention, the photosensitive resin composition layer 5 containing the phosphor (A), which has each of the phosphors that emit red, green, and blue independently, has a different color for each of red, green, and blue. It can be performed in any order.

The steps (I) to (III) of the present invention were repeated for each color to form a multicolor pattern composed of a photosensitive tree composition containing a phosphor emitting red, green and blue colors. The state is shown in FIG. In FIG. 6, 5'a is the first color pattern, 5'b is the second color pattern, and 5'c is the third color pattern.

FIG. 7 shows a state where a multicolor pattern is formed by performing the step (IV) in the present invention. In addition,
In FIG. 7, reference numeral 10a denotes a first color phosphor pattern;
b is the phosphor pattern of the second color and 10c is the phosphor pattern of the third color.

Further, the method for producing a phosphor pattern of the present invention comprises:
From the viewpoint of suppression of film thinning and the like, (I) to (I) in the present invention.
It is preferable that the steps (IV) are repeated for each color to form a multicolor phosphor pattern that emits red, green and blue.

[0153]

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

Production Example 1 [Preparation of Polymer Binder Solution (a-1)] (1) shown in Table 1 was placed in a flask equipped with a stirrer, a reflux condenser, an inert gas inlet tube and a thermometer. 8 under nitrogen gas atmosphere
The temperature was raised to 0 ° C., and while maintaining the reaction temperature at 80 ± 2 ° C., (2) shown in Table 1 was dropped uniformly over 4 hours.

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

[0156]

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

[0157]

[Table 2] The resulting solution was uniformly coated on a 20 μm-thick polyethylene terephthalate film, and dried with a hot air convection dryer at 80 to 110 ° C. for 10 minutes to remove the solvent.
(A) A photosensitive resin composition layer containing a phosphor was formed. The thickness of the obtained photosensitive resin composition layer containing the phosphor (A) after drying was 50 μm.

Next, a 25 μm-thick polyethylene film is laminated as a cover film on the (A) phosphor-containing photosensitive resin composition layer, and (A) the phosphor-containing photosensitive resin composition A photosensitive element (A-1) including a layer was prepared.

Production Example 3 [(B) Preparation of Solution (B-1) for Thermoplastic Resin Layer] Table 3
(B) A solution for a thermoplastic resin layer was prepared. The obtained solution was uniformly coated on a polyethylene terephthalate film having a thickness of 20 μm,
The solvent was removed by drying with a hot air convection dryer at 10 ° C. for 10 minutes to form (B) a thermoplastic resin layer. The thickness of the obtained (B) thermoplastic resin layer after drying was 50 μm.

Next, a polyethylene film having a thickness of 25 μm was laminated as a cover film on the thermoplastic resin layer (B) to prepare a photosensitive element (B-1) containing the thermoplastic resin layer (B). .

[0161]

[Table 3] Example 1 [(I) Step of Forming (A) Photosensitive Resin Composition Layer Containing Phosphor on Irregular Surface of Plasma Display Panel Substrate Formed with Barrier Rib] PDP Substrate (Striped Barrier Rib, Barrier Rib) 150μ opening width
m, barrier rib width 70 μm, barrier rib height 150
The photosensitive element (A-1) containing the (A) phosphor-containing photosensitive resin composition layer obtained in Production Example 2 on the side on which the barrier rib of (μm) was formed, while peeling off the polyethylene film, Vacuum laminator (Hitachi Chemical Industries, Ltd.)
And a laminating speed of 1.5 m / min. And a pressure of 40.degree.
00Pa or less, pressure pressure is 2.5 × 10 ³ N / m in linear pressure
Was laminated.

Next, the polyethylene terephthalate film of the photosensitive element (A-1) including the photosensitive resin composition layer containing the phosphor (A) is peeled off, and the photosensitive resin composition containing the phosphor (A) is removed. On the layer, the film (B-1) containing the thermoplastic resin layer (B) obtained in Production Example 3 was
While peeling off the polyethylene film, using a laminator (trade name: HLM-3000, manufactured by Hitachi Chemical Co., Ltd.), the laminating temperature is 110 ° C., the laminating speed is 0.5 m / min, and the pressing pressure is a linear pressure of 5 ×. Lamination was performed at 10 ³ N / m.

[(II) Step of irradiating actinic rays imagewise] Next, (B) a film containing a thermoplastic resin layer (B-
A photomask for testing is adhered to the polyethylene terephthalate film of 1), and the H mask manufactured by Oak Manufacturing Co., Ltd.
Using an MW-201GX type exposure machine, 100 mJ / cm
^{In step 2} , actinic rays were irradiated imagewise.

[(III) Step of Removing Unwanted Parts by Development] Then, after irradiation with actinic rays, the mixture was allowed to stand at room temperature for 1 hour, and then 30 ° C. using a 1% by weight aqueous solution of sodium carbonate using ion-exchanged water. For 120 seconds. After the development, the film was dried at 100 ° C. for 10 minutes, and 3 J / cm ² using a Toshiba UV irradiator manufactured by Toshiba Electric Materials Co., Ltd.
And then heated at 150 ° C. for 30 minutes.

The iron ion in the developer was 2 ppm, the sulfate ion was 2 ppm, the sulfite ion was 4 ppm, the nitrate ion was 5 ppm, the nitrite ion was 4 ppm, the chloride ion was 4 ppm, and the chlorine was 100 ppm.

[(IV) Step of Removing Unwanted Parts by Firing] Then, a heat treatment (firing) is performed at 480 ° C. for 20 minutes to remove unnecessary resin components, and a phosphor pattern is formed in the space of the PDP substrate. Formed.

Comparative Example 1 The procedure of Example 1 was repeated, except that the developer used in [(III) Step of Removing Unwanted Parts by Development] was changed to a 1% by weight aqueous solution of sodium carbonate using tap water. 1
A phosphor pattern was formed in the same manner as described above.

The iron ion in the developer was 800 ppm.
Sulfate ion was 2 ppm, sulfite ion was 4 ppm, nitrate ion was 5 ppm, nitrite ion was 4 ppm, chloride ion was 300 ppm, and chlorine was 600 ppm.

[Evaluation of Luminance Luminance of Phosphor Pattern] Only the phosphor of the phosphor pattern obtained in Example 1 and Comparative Example 1 was taken out, and the phosphor powder was formed into a pellet with a molding machine, and the wavelength was 254 nm. And the emitted visible light was measured with a luminance meter. The untreated phosphor was heated at 480 ° C. for 20 minutes, formed into a pellet, irradiated with ultraviolet light having a wavelength of 254 nm, and the emitted visible light was measured with a luminance meter. When the rate of decrease in the emission luminance of only the phosphor of the phosphor pattern obtained as described above was determined, the decrease in the emission luminance of the phosphor pattern was 1% in Example 1, but in Comparative Example 1, It decreased by 30%. From this result, it is understood that the emission luminance of the phosphor pattern formed using the developing solution of the present invention is hardly reduced. On the other hand, it can be seen that the emission luminance of the phosphor pattern formed without using the developing solution of the present invention is significantly reduced.

[0170]

According to the present invention, a phosphor pattern having a uniform shape with high precision can be formed with good workability, and the phosphor luminance can be prevented from deteriorating when emitted as a PDP.

[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 an example of a schematic view showing a state in which a photosensitive resin composition layer containing a phosphor is formed.

FIG. 6 is a schematic diagram showing a state in which a multicolor pattern formed of a photosensitive resin composition layer containing a phosphor is formed.

FIG. 7 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 Grating discharge space 4 Stripe discharge space 5 Photosensitive resin composition layer having phosphor 5 ′ Photosensitive resin composition layer having phosphor after photocuring 5′a First color pattern 5 ′ b 2nd color phosphor pattern 5′c 3rd color phosphor pattern 6 thermoplastic resin layer 7 heating roll 8 photomask 9 actinic ray 10 phosphor pattern 10a 1st color phosphor pattern 10b 2nd color phosphor pattern 10c 3 Color phosphor pattern

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tsuyoshi Nojiri 4-3-1, Higashicho, Hitachi City, Ibaraki Prefecture Inside Hitachi Chemical Co., Ltd. 1 Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd. (72) Inventor Seiji Tai 4-13-1, Higashicho, Hitachi City, Ibaraki Prefecture Within Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd. 4-13-1, Hitachi Chemical Co., Ltd., Yamazaki Plant (72) Inventor Katsutoshi Itagaki 4-13-1, Higashicho, Hitachi City, Ibaraki Prefecture, Hitachi Chemical Co., Ltd., Yamazaki Plant

Claims (1)

[Claims] (I) a step of forming a photosensitive resin composition layer containing a phosphor on a substrate for a plasma display panel on which barrier ribs are formed, and (II) a photosensitive resin composition containing a phosphor. Irradiating the layer with actinic rays imagewise, (III) selectively removing unnecessary portions of the photosensitive resin composition layer containing the phosphor by development to form a pattern, and (IV) forming a pattern from the pattern. In a method for manufacturing a back plate for a plasma display panel, the method includes a step of forming a phosphor pattern by removing unnecessary components by firing.
II) In the step of selectively removing unnecessary portions of the phosphor-containing photosensitive resin composition layer by development to form a pattern, the step of transition metal ions, sulfate ions, sulfite ions,
A method for producing a back plate for a plasma display panel, comprising using a developing solution in which each content of nitrate ion, nitrite ion, chloride ion and chlorine is less than 500 ppm by weight.