JPH11242327A - Photosensitive element, its production, production of phosphor pattern using photosensitive element, phosphor pattern, and back plate for plasma display panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive element in which a phosphor pattern of high accuracy and uniform shape can be formed with good workability, to provide its producing method, a producing method of a phosphor pattern, and a back plate for a plasma display panel having the phosphor pattern. SOLUTION: This photosensitive element consists of a first supporting film 5, (A) a peelable embedded layer 6 on the film 5, (B) an intermediate layer 7 on the layer 6, and (C) a photosensitive resin compsn. layer (compsn. layer) 8 containing a phosphor on the layer 7. This photosensitive element is produced in the following process. A first element having (A) a peelable embedded layer 6 on a first supporting film 5 and further having (B) an intermediate layer 7 on the layer 6 is laminated on a second element having (C) a compsn. layer 8 on a second supporting film, with the (B) intermediate layer 7 and the (C) compsn. layer facing each other. Then the second supporting film is removed by peeling.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive element, a method for manufacturing the same, a method for manufacturing a phosphor pattern using the photosensitive element, a phosphor pattern, and 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 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 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-1-15027, JP-A-1-124929, and JP-A-1-124930. 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 liable 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 of using the photosensitive element is that the photosensitive resin composition layer containing the phosphor of the photosensitive element composed of the photosensitive resin composition layer containing the phosphor and the support film is heat-pressed (laminated). It is embedded in the space of the substrate for PDP, and then imagewise exposed to active light such as ultraviolet light by a photographic method using a negative film,
An unexposed portion is removed with a developing solution such as an aqueous alkaline solution, and unnecessary organic components are removed by baking to form a phosphor pattern only on a necessary portion. Therefore, when a phosphor pattern is formed in the space of the PDP substrate, it is not necessary to confirm the dispersibility of the phosphor, and the phosphor has excellent storage stability as compared with the phosphor dispersion slurry or paste. I have. Furthermore, since a photographic method is used, a phosphor pattern can be formed with high accuracy.

However, a photosensitive element composition layer containing a phosphor is prepared by using a photosensitive element by a conventional method.
When embedded in the space (in the cell) of the PDP substrate by lamination, it was difficult to form a phosphor pattern with a uniform layer thickness and shape on the barrier rib wall surface and the space bottom surface. On the other hand, lamination using a laminate of a photosensitive resin composition layer containing a phosphor and an embedding layer has been proposed. In the bonding of the phosphor-containing photosensitive resin composition layer and the burying layer, which has been proposed as one of the manufacturing methods of the laminate used in this method, the phosphor-containing photosensitive resin composition layer and the burying layer are embedded. Adhesion with layer is small,
There is a problem that it is difficult to maintain a laminated structure as a photosensitive element.

[0006]

SUMMARY OF THE INVENTION The invention according to claim 1 relates to the laminating property of each layer and the embedding property of a substrate having irregularities such as a PDP substrate in a concave portion (for a PDP substrate, the rib wall surface and the substrate surface). Of the photosensitive resin composition layer containing the phosphor in the recesses (corresponding to the discharge space) corresponding to the discharge space composed of the above, and form a phosphor pattern having a uniform shape with high precision with good workability. The present invention provides a photosensitive element that can be used. The invention according to claim 2 provides a method for producing a photosensitive element having excellent workability and stability.

According to a third aspect of the present invention, there is provided a method of embedding a substrate having irregularities such as a PDP substrate in a concave portion (for a PDP substrate, a concave portion corresponding to a discharge space formed by rib wall surfaces and a substrate surface). The present invention provides a method for producing a phosphor pattern capable of forming a phosphor pattern having a uniform shape with high accuracy and excellent sensitivity (corresponding to a discharge space). The invention described in claim 4 provides a method of manufacturing a phosphor pattern that is further excellent in workability and environmental safety in addition to the effects of the invention described in claim 3. The fifth aspect of the present invention is to provide a phosphor pattern having high accuracy, uniform shape, and excellent luminance. A sixth aspect of the present invention is to provide a back plate for a plasma display panel provided with a phosphor pattern having a high accuracy, a uniform shape, and an excellent luminance.

[0008]

According to the present invention, there is provided a first support film having (A) a releasable buried layer, a (B) mediating layer thereon, and a further (C) The present invention relates to a photosensitive element having a photosensitive resin composition layer containing a phosphor. The present invention also provides a first element having (A) a peelable buried layer on a first support film, and further having (B) an intermediate layer formed thereon, and a second support. A second element having a (C) phosphor-containing photosensitive resin composition layer on a body film, a (B) mediating layer and a (C) phosphor-containing photosensitive resin composition layer The present invention relates to the above-mentioned method for producing a photosensitive element, characterized in that, after laminating so as to face each other, the second support film is peeled off and removed.

The present invention also provides (I) a step of laminating the photosensitive element on a substrate having irregularities such that a photosensitive resin composition layer containing a phosphor (C) is in contact with the substrate; (II) (A) Peelable embedded layer and first layer
(III) (C) irradiating the photosensitive resin composition layer containing the phosphor imagewise with actinic light, (IV) imagewise irradiating actinic light by development (C) the step of selectively removing the phosphor-containing photosensitive resin composition layer to form a pattern comprising the phosphor-containing photosensitive resin composition; and (V) baking the pattern to obtain a fluorescent light. The present invention relates to a method for producing a phosphor pattern, comprising a step of forming a body pattern. In addition, the present invention is characterized in that each of the steps (I) to (IV) is repeated for each photosensitive element having a photosensitive resin composition layer containing a phosphor that emits red, green and blue, respectively. After forming a multicolor pattern made of a photosensitive resin composition containing a phosphor that emits green and blue, the step of (V) is performed to form a multicolor phosphor pattern. Related to manufacturing method.

[0010] The present invention also relates to a phosphor pattern manufactured by the above-described method for manufacturing a phosphor pattern. The present invention also relates to a plasma display panel back plate comprising the above-described phosphor pattern on a plasma display panel substrate.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive element of the present invention has (A) a peelable embedding layer on a first support film, (B) an intermediate layer thereon, and further comprises (C) A photosensitive resin composition layer containing a phosphor is provided thereon. As the first support film,
For example, polyethylene terephthalate, polycarbonate, polyethylene, thickness 5 consisting of polypropylene and the like
A film having a thickness of about 300 μm is exemplified.

In order to facilitate the removal of the first support film together with the (A) peelable burying layer,
A layer having a thickness of about 1 to 50 μm for improving the adhesiveness of the (A) peelable embedment layer to the first support film is provided between the support film and the (A) peelable burying layer. Further, it can be provided. Specific examples of the material constituting this layer include ethylene and 20% by weight or less of an alkyl (meth) acrylate copolymer, ethylene and 20% by weight or less of a vinyl alkanoate copolymer, and propylene and 20% by weight.
Wt.% Or less of an alkyl (meth) acrylate copolymer, and a copolymer of propylene and an unsaturated monomer such as 20 wt.% Or less of a vinyl alkanoate copolymer. Melt extrusion coating on the first support film can be performed.

The peelable burying layer (A) in the present invention is deformed by an external stress when the photosensitive element of the present invention is laminated, and (C) the photosensitive resin containing the phosphor in the photosensitive element of the present invention. By pressing the composition layer, the photosensitive resin composition layer containing the (C) phosphor is contained in the concave portion thereof while ensuring good follow-up of the unevenness on the substrate having the unevenness. (C) After the photosensitive resin composition layer containing the phosphor is laminated, the photosensitive resin composition layer is removed by peeling or the like. Is done.

The material constituting the peelable buried layer (A) in the present invention is not particularly limited as long as it can be deformed by an external stress.
For example, polycarbonate, polyurethane, rubbers (butadiene rubber, styrene-butadiene rubber, silicon rubber, etc.), polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride, polystyrene, polyvinyl toluene, polyacrylate, polymethacrylate, ethylene 20% by weight or more of vinyl acetate copolymer, ethylene and 20% by weight or more of acrylate ester copolymer, vinyl chloride and 20% by weight or more of vinyl acetate copolymer, styrene and 20% by weight or more of acrylic Copolymers of acid esters or methacrylic esters, copolymers of vinyl toluene and 20% by weight or more of acrylic esters or methacrylic esters, polyvinyl alcohol resins (hydrolysates of polyvinyl acetate, ethylene and vinyl acetate Hydrolyzate of copolymer with Such as hydrolysis, etc.) of a copolymer of vinyl chloride and vinyl acetate. These are used alone or in combination of two or more.

In the present invention, (A) the peelable burying layer is a photopolymerizable resin having an ethylenically unsaturated group (b) contained in a photosensitive resin composition layer containing a phosphor (C) described later. An organic low-molecular-weight compound such as an unsaturated compound, (c) a photoinitiator that generates free radicals upon irradiation with active light, or other additives can also be contained. In the present invention, the thickness of the (A) peelable embedding layer is 20
To 200 μm, preferably 30 to 100 μm
Is more preferable.

The mediating layer (B) according to the present invention is provided between the (A) peelable embedding layer and the (C) photosensitive resin composition layer containing the phosphor in the photosensitive element of the present invention. (C) a photosensitive resin composition layer containing a phosphor (C) until the photosensitive element of the present invention has a suitable adhesiveness to both layers and is completely laminated on the uneven substrate. After the photosensitive element of the present invention is laminated on a substrate having irregularities, (A) has a function of temporarily holding the phosphor so as not to be peeled off from the peelable embedded layer, and This is a layer that does not prevent the (A) peelable buried layer from being removed from the photosensitive resin composition layer containing.

(B) The material constituting the mediating layer is not particularly limited as long as the above properties can be satisfied.
(C) a film-forming polymer and (e) a number average molecular weight of 160 to 10,000, preferably 400 to 500, which constitute a photosensitive resin composition layer containing a phosphor described below.
It is preferable to include a compound having a polyoxyalkylene chain having 0 carbon atoms (the alkylene portion has 2 to 6, preferably 2 to 3, and may be linear or branched).

Among the compounds of the above (e), the following general formula (I)

Embedded image (Wherein, R represents a hydrogen atom or a methyl group, Y ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Y ² represents a hydroxyl group or an alkyl group having 1 to 6 carbon atoms, and p represents 1-100
Is preferable, and specific examples thereof include, for example, polypropylene glycol dimethyl ether, polypropylene glycol diethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol diethyl ether, polypropylene glycol, polyethylene glycol, and polybutylene glycol. Can be

In the present invention, the mediating layer (B) includes:
(C) a photopolymerizable unsaturated compound having an ethylenically unsaturated group contained in a photosensitive resin composition layer containing a phosphor described below, and (c) light that generates free radicals upon irradiation with active light. An initiator, a commercially available surfactant, and other additives can be contained.

The compounding amount of the compound (e) is preferably 1 to 200 parts by weight, more preferably 1 to 170 parts by weight, more preferably 1 to 170 parts by weight, based on 100 parts by weight of the component (a). Particularly preferred is 150 parts by weight. If the amount is less than 1 part by weight, the adhesiveness of the mediating layer (B) tends to be too low, and if it exceeds 200 parts by weight, the fluidity becomes too high to be liquid and it is difficult to form the mediating layer (B). It tends to be. In the present invention, (B) the thickness of the mediating layer is 1
The thickness is preferably from 50 to 50 μm, more preferably from 2 to 40 μm.

The photosensitive resin composition layer containing the phosphor (C) in the present invention is not particularly limited in its composition, and may be constituted by using a known photosensitive resin composition used in a photolithographic method. Is (can be adjusted by adding a phosphor to a known photosensitive resin composition), from the viewpoint of photosensitivity and workability,
(A) a film imparting polymer, (b) a photopolymerizable unsaturated compound having an ethylenically unsaturated group, (c) a photoinitiator that generates free radicals upon irradiation with active light, and (d) a phosphor. Is preferred. As the photosensitive resin composition containing such a phosphor, for example, those described in JP-A-9-265906 can be applied.

As the polymer (a) for imparting film property, a vinyl copolymer is preferable. Examples of the vinyl monomer used for the vinyl copolymer include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate. ,
Ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, acrylic Octyl acid,
Octyl methacrylate and the like can be mentioned. These are used alone or in combination of two or more.

(A) The weight average molecular weight of the film imparting polymer is preferably from 5,000 to 300,000, more preferably from 20,000 to 150,000. If the weight average molecular weight is less than 5,000, the film formability and flexibility of the photosensitive element tend to decrease, and if it exceeds 300,000, the developability (unnecessary portions are easily developed by development). Tend to be reduced). The weight average molecular weight is a value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve.

Also, (a) the carboxyl group content (acid value (A) of the polymer imparting film properties) is adjusted so that the photosensitive resin composition layer containing the phosphor (C) can be developed with various known developers. mgKOH / g) can be adjusted as appropriate. For example, when developing using an aqueous alkali solution such as sodium carbonate or potassium carbonate, the acid value is preferably from 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.

Examples of the photopolymerizable unsaturated compound (b) having an ethylenically unsaturated group include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, and triethylene glycol diacrylate. Ethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, hexapropylene glycol diacrylate, hexapropylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, butylene Glycol glycol , Butylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 2,2-bis (4
-Acryloxyethoxyphenyl) propane, 2,2-
Bis (4-methacryloxyethoxyphenyl) propane, 2,2-bis (4-acryloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloxydiethoxyphenyl) propane, 2,2-bis (4 -Acryloxypolyethoxyphenyl) propane, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, tetramethylolpropane Examples include tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol tetraacrylate, and pentaerythritol tetramethacrylate.
These are used alone or in combination of two or more.

Examples of the photoinitiator (c) that generates free radicals upon irradiation with active 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 derivative (benzyl dimethyl ketal, etc.), 2 , 4,5 Triarylimidazole dimer (2-(o-chlorophenyl) -4,5-diphenyl imidazole dimer, 2-(o-chlorophenyl) -
4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl)-
4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, -(2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer and the like, and acridine derivatives (9-phenylacridine,
1,7-bis (9,9'-acridinyl) heptane and the like
And the like. These are used alone or in combination of two or more.

The phosphor (d) 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, YVO ₄ : Eu,
(Y, Gd) BO ₃ : Eu, γ-Zn ₃ (PO ₄ ) ₂ : Mn,
(ZnCd) S: Ag + In ₂ O and the like. Examples of green-colored phosphors include ZnS: Cu and Zn ₂ S.
iO ₄ : Mn, ZnS: Cu + Zn ₂ SiO ₄ : Mn, G
d 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, Tb, BaO · 6
Al ₂ O ₃ : Mn and the like. Examples of blue-colored phosphors include ZnS: Ag, ZnS: Ag, Al, and Z.
nS: Ag, Ga, Al, ZnS: Ag, Cu, Ga,
Cl, ZnS: Ag + In ₂ O ₃ , Ca ₂ B ₅ O ₉ Cl: E
u ²⁺ , (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : E
u ²⁺ , Sr ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu ²⁺ , BaMgAl ₁₀
O ₁₇ : Eu ²⁺ , BaMgAl ₁₄ O ₂₃ : Eu ²⁺ , BaMg
Al ₁₆ O ₂₆ : Eu ^{2+ and the} like.

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

The amount of the component (a) is 10 to 90 parts by weight based on 100 parts by weight of the total amount of the components (a) and (b).
The weight is preferably set to 20 parts by weight, more preferably 20 to 80 parts by weight. When the compounding amount is less than 10 parts by weight, when the photosensitive element is supplied in a roll form,
By exuding the photosensitive resin composition containing the phosphor from the end of the roll (hereinafter referred to as edge fusion),
When the photosensitive element is laminated, it is difficult to draw out from the roll, and the extruded 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 problem of film formation. When the content exceeds 90 parts by weight, the sensitivity tends to be insufficient.

The amount of the component (b) is from 10 to 90, based on 100 parts by weight of the total amount of the components (a) and (b).
The weight is preferably set to 20 parts by weight, more preferably 20 to 80 parts by weight. 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, and 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 decrease.

The amount of the component (c) is from 0.01 to 100 parts by weight of the total of the components (a) and (b).
Preferably it is 30 parts by weight, more preferably 0.1 to 20 parts by weight. If the amount is less than 0.01 part by weight, the sensitivity of the photosensitive resin composition containing the phosphor tends to be insufficient, and if it 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 500 parts by weight based on 100 parts by weight of the total of the components (b) and (c).
400 parts by weight, more preferably 10 to 300 parts by weight.
It is particularly preferred that the amount be from 50 to 250 parts by weight. When the compounding amount is less than 10 parts by weight, the luminous efficiency tends to decrease when light is emitted as a PDP, and when it exceeds 500 parts by weight, when a photosensitive element is used, the film formability decreases, Flexibility tends to decrease.

In the present invention, the photosensitive resin composition constituting the photosensitive resin composition layer containing the phosphor (C) includes a dye, a color former, a plasticizer, a pigment, a polymerization inhibitor, a surface modifier, Agents, stabilizers, adhesion-imparting agents, thermosetting agents, and the like can be added as necessary.

The thickness of the photosensitive resin composition layer containing the phosphor (C) in the present invention is not particularly limited.
The thickness is preferably 200 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 decreases. As a result, the luminous efficiency tends to decrease.

The photosensitive element of the present invention comprises, for example, a first element having (A) a peelable embedded layer on a first support film, and (B) an intermediate layer formed thereon. A second element comprising a (C) phosphor-containing photosensitive resin composition layer on a second support film and a (B) mediating layer and (C) a phosphor containing the phosphor. Peeling and removing the second support film between the second support film and the photosensitive resin composition layer containing the phosphor (C) after laminating so that the conductive resin composition layers face each other. Can be manufactured.

First, the first element (according to claim 1)
Can be produced as follows. (A) The peelable embedding layer is formed by dissolving the resin and the like constituting the same in a solvent capable of dissolving them, thereby obtaining a uniformly dissolved solution. Obtained by drying.

Examples of the solvent for dissolving the material constituting the peelable embedded layer (A) include toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, γ-butyrolactone, N-methylpyrrolidone, and the like. Dimethylformamide, tetramethylsulfone, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, chloroform, methylene chloride, methyl alcohol,
Ethyl alcohol and the like can be mentioned. These are used alone or in combination of two or more.

As the coating method, known methods can be used, for example, 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. The drying temperature is 6
The temperature is preferably from 0 to 130 ° C, and the drying time is preferably from 3 minutes to 1 hour.

The (B) mediating layer is made into a uniformly dissolved solution by dissolving the resin or the like constituting the (B) mediating layer in a solvent capable of dissolving, and (A) is formed on the peelable embedded layer. , Coating and drying. As the solvent for dissolving the material constituting the (B) mediating layer,
The above-mentioned solvent is mentioned, and the above-mentioned method is mentioned as the above-mentioned application method. A releasable cover film may be further laminated on the (B) mediating layer. Such a cover film has a thickness of 5 to 5.
A film having a thickness of about 5 to 100 μm made of polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, or the like having a thickness of about 100 μm is included. The adhesive strength between the support film and the (B) mediating layer is smaller than that of the cover film and the (B) mediating layer. It is preferable to select and use a material having a smaller adhesive force with the adhesive. The first element thus obtained can be stored in a roll.

On the other hand, the second element (according to claim 2) is obtained as follows. The second support film has the same material and form as the first support film. (C) The photosensitive resin composition layer containing the phosphor is dissolved or mixed in a solvent capable of dissolving or dispersing the components constituting the phosphor to form a uniformly dispersed solution,
It is obtained by coating and drying on a second support film. Examples of the solvent capable of dissolving or dispersing the above components include the above-mentioned solvents. Examples of the coating method include the methods described above.

A releasable cover film may be further laminated on the photosensitive resin composition layer containing the phosphor (C). As such a cover film, polyethylene, polypropylene, polyethylene terephthalate, a thickness of
A film having a thickness of about 100 μm is used. The adhesive strength between the support film and the photosensitive resin composition layer containing the phosphor (C) is smaller than the cover film and the photosensitive resin composition layer containing the phosphor (C). It is preferable to select and use a material having a smaller adhesive force with the adhesive. The second element thus obtained can be stored in a roll.

The first element and the second element are
As a method of laminating so that the (B) mediating layer and the (C) phosphor-containing photosensitive resin composition layer face each other, when each photosensitive element has a cover film, it is peeled off and removed. Meanwhile, it can be performed by pressure bonding with a laminator or the like. In this case, the pressing pressure of the laminating roll is preferably 50 to 1 × 10 ⁵ N / m, more preferably 2.5 × 10 ^{2 to} 5 × 10 ⁴ N / m in linear pressure, It is particularly preferred to be 5 × 10 ² to 4 × 10 ⁴ N / m. If the pressure is less than 50 N / m, it may not be possible to adhere sufficiently, and 1 × 10 ⁵ N / m
Is exceeded, the photosensitive element tends to cause edge fusion. After laminating the first element and the second element, (C) the second support film on the photosensitive resin composition layer containing the phosphor is peeled off to obtain the photosensitive element of the present invention. Can be

In the phosphor pattern of the present invention, (I) a step of laminating the photosensitive element on a substrate having irregularities such that the photosensitive resin composition layer containing the phosphor (C) is in contact with the substrate. (II) (A) removing the peelable embedded layer together with the first support film, (III)
(C) a step of imagewise irradiating the photosensitive resin composition layer containing the phosphor with actinic light, and (IV) a photosensitive resin containing the phosphor (C) which is imagewise irradiated with actinic light by development. (B) selectively removing the composition layer together with the mediating layer to form a pattern made of a photosensitive resin composition containing a phosphor, and (V) firing the pattern to form a phosphor pattern At least.

Examples of the substrate having irregularities in the present invention include a substrate for a plasma display panel (substrate for PDP) on which barrier ribs are formed. As the PDP substrate, for example, a glass plate, a synthetic resin plate, or the like having a thickness of 0.5, which may be subjected to a surface treatment for transparent bonding.
An example is a substrate in which electrodes and barrier ribs are formed on a substrate of about 5 mm. For the formation of the barrier rib, a known material can be used without any particular limitation. For example, silica,
A rib material containing 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 the barrier ribs, a dielectric film, an insulating film, an auxiliary electrode, a resistor, and the like may be formed on the PDP substrate as necessary.

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 height and width of the barrier rib are respectively about 20 to 500 μm and about 20 to 200 μm. The shape of the discharge space surrounded by the barrier ribs
There is no particular limitation, lattice, stripe, honeycomb,
Although a triangular shape, an elliptical shape, and the like can be used, a grid-like or stripe-like discharge space is often formed as shown in FIGS. 1 and 2, a barrier rib 2 is formed on a substrate 1. In FIG. 1, a grid-like discharge space 3 is formed, and in FIG. 2, a stripe-like discharge space 4 is formed. The size of the discharge space is determined by the size and resolution of the PDP. Generally, in the case of a grid-like discharge space as shown in FIG. 1, the vertical and horizontal lengths are 50 μm to 1 mm, and the stripe as shown in FIG. In the case of a discharge space, the interval is 30 μm to 1 mm.

Hereinafter, an example of the production of the phosphor pattern of the present invention will be described with reference to FIGS. FIGS. 3 and 4 are schematic views showing each step of manufacturing the phosphor pattern of the present invention.

[(I) a step of laminating the photosensitive element according to claim 1 on a substrate having irregularities so that the photosensitive resin composition layer containing the phosphor (C) is in contact with the substrate] The photosensitive element of the present invention is arranged so that the photosensitive resin composition layer containing the phosphor (C) faces the substrate having the unevenness, and pressure is applied to the first support film to obtain C) The photosensitive element of the present invention having a photosensitive resin composition layer containing a phosphor is laminated on a substrate having irregularities. An example of this (I) step is shown in FIG.
This is shown in (I) and FIG. 3 (II).

FIG. 3 (I) shows a case where the photosensitive resin composition layer 8 containing the phosphor (C) faces the PDP substrate 1 (substrate having irregularities) on which the barrier ribs 2 are formed. 1 shows a state in which the photosensitive element of the invention is arranged. In this case, when a cover film is present on the photosensitive element, the cover film can be removed and then laminated. FIG. 3 (II) shows the PDP substrate 1 by applying pressure to the first support film 5 in the state of FIG. 3 (I).
(C) The photosensitive resin composition layer 8 containing a phosphor, the (B) mediating layer and the (A) peelable embedding layer are pressed against the surface on which the barrier rib 2 is formed, and the PDP on which the barrier rib 2 is formed (C) Photosensitive resin composition layer 8 containing phosphor, (B) mediating layer 7 and (B) into space (concave portion) surrounded by barrier rib wall surface and substrate bottom surface of substrate 1 (substrate having irregularities). A) shows a state in which the peelable burying layer 6 is buried.

In FIG. 3 (II), as a method of pressure bonding, for example, a method of pressing with a pressure roll 9 or the like can be mentioned. The pressure at this time was 2.4 × 10 in linear pressure.
It is preferably set to ^{2 to} 2.4 × 10 ⁵ N / m, and 4.8 × 10 ⁵ N / m is preferable.
It is more preferable to be 10 ^{2 to} 1.2 × 10 ⁵ N / m,
It is particularly preferred to be 9.6 × 10 ^{2 to} 2.4 × 10 ⁴ N / m. If this pressure is less than 2.4 × 10 ² N / m,
(C) PDP of photosensitive resin composition layer 8 containing phosphor
1. There is a tendency that the embedding property of the substrate into the concave portion is reduced.
If it exceeds 4 × 10 ⁵ N / m, the barrier rib of the PDP substrate tends to be broken. Further, in order to further improve the embedding property of the photosensitive resin composition layer 8 containing the phosphor in the space, the surface of the pressure roll is made of a material such as rubber or plastic which is rich in flexibility. Can also be used. The thickness of the layer made of a material having a high flexibility is 2
It is preferable to set it to 00 to 400 μm.

In order to further improve the embedding property of the photosensitive resin composition layer 8 containing the phosphor into the space (C), the surface of the PDP substrate on which the barrier ribs are formed while being heated by a heating roll or the like. It can also be laminated by pressing. The heating temperature at the time of heating is preferably 10 to 140 ° C, more preferably 20 to 135 ° C, and particularly preferably 30 to 130 ° C. If the heating temperature is lower than 10 ° C., the embeddability of the photosensitive resin composition layer 8 containing the phosphor (C) into the space of the PDP substrate tends to decrease.
(C) The photosensitive resin composition layer 8 having a phosphor tends to be cured by heat.

If the substrate is heated by a heating roll or the like as described above, it is not particularly necessary to pre-heat the PDP substrate, but (C) the photosensitive resin composition layer 8 containing the phosphor
In order to further improve the embedding property of the
It is preferable that the substrate for P is pre-heat treated. The preheating temperature at this time is preferably 30 to 140 ° C., and
The preheating time is preferably 0.5 to 20 minutes.
Further, for the same purpose, under reduced pressure of 5 × 10 ⁴ Pa or less,
The operations of the above-mentioned compression bonding and thermal compression bonding can also be performed.
After the lamination is completed, 1 to 30 ° C.
Heating for ~ 120 minutes can also be used.

Thus, the photosensitive resin composition layer 8 containing the phosphor (C) can be uniformly formed on the surface of the concave portion of the PDP substrate. Also described later (II)
(A) In the step of removing the peelable embedded layer,
(A) After the step (I), the PDP substrate is cooled (−50) in order to facilitate the peeling of the peelable embedded layer.
~ 50 ° C). In addition, a combination of the above-described heating conditions during the thermocompression bonding, the pressure bonding pressure conditions, the preheating conditions of the PDP substrate, and (B) the intermediate layer and / or (A) the film thickness of the peelable embedded layer 6 and the like. By changing the number of layers, the layers can be stacked 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.

[(II) (A) Step of Removing the Peelable Embedding Layer and the First Support Film] (A) FIG. 3 (III) shows a state in which the peelable embedding layer 6 has been peeled off. In FIG. 3 (III), as a method for removing the (A) peelable embedded layer 6, for example, (A) the first support film 5 having the peelable embedded layer 6 may be
A method of bonding an adhesive tape or physically peeling it off using a hook-shaped jig or the like can be given. Further, for the purpose of improving workability, a method of (A) peeling off the peelable buried layer 6 using a force such as static electricity or suction may be used.

[(III) Step of irradiating (C) phosphor-containing photosensitive resin composition layer imagewise with actinic ray] Actinic ray 11 is applied to (C) phosphor-containing photosensitive resin composition layer 8
FIG. 3 (IV) shows a state where the image is irradiated imagewise. FIG. 3 (I
In V), the method of imagewise irradiating the actinic ray 11 is to imagewise irradiate the actinic ray 11 through a photomask 10 such as a negative film or a positive film in the state of FIG. Can be. The actinic ray 11 can be imagewise irradiated with the (B) mediating layer removed, in which case (C) the photosensitive resin composition layer 8 containing the phosphor.
The above-mentioned support film may be newly coated on the substrate, and the actinic ray 11 may be irradiated imagewise.

The transmission width of the actinic light 11 of the photomask 10 is usually the opening width of the concave portion of the PDP substrate. In the step (I), the light is transmitted as shown in FIG. In this case, it is preferable that the transmission width is the same as the opening width of the concave portion of the PDP substrate, or the transmission width is smaller than the opening width of the concave portion of the PDP substrate, from the viewpoint of increasing the margin of the positioning accuracy. On the other hand, in the case of laminating as shown in FIG. 5 in the step (I), it is preferable that the transmission width narrower than the opening width of the concave portion of the PDP substrate is set on the barrier rib by an undesired photocured phosphor. From the viewpoint that the latitude of positioning accuracy can be increased without leaving a photosensitive resin composition layer containing

The actinic rays 11 include, for example, light generated from a carbon arc, a mercury vapor arc, a xenon arc, and the like. Further, the actinic ray 11 in the present invention
May be parallel rays or scattered rays. Further, the irradiation amount of the actinic ray 11 in the present invention is not particularly limited, but is preferably 5 to 10000 mJ / cm ^2, and more preferably 7 to 5000 mJ / cm ² from the viewpoint of photocurability and the like. It is particularly preferably 10 to 3000 mJ / cm ² .

[(IV) Step of forming a pattern by selectively removing the photosensitive resin composition layer containing the phosphor, which is imagewise irradiated with actinic rays by development (C)] This is shown in FIG. Note that in FIG.
8 'is a photosensitive resin composition layer containing a phosphor after photocuring. Here, the (C) photosensitive resin composition layer containing the phosphor, which has been image-irradiated with actinic rays, is removed together with the (B) mediating layer. In FIG. 4 (V), as a developing method, for example, after the state of FIG. 3 (IV), using a known developing solution such as an alkaline aqueous solution, an aqueous developing solution, and an organic solvent,
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 can be given. In addition, (C) a method of removing unnecessary portions of the photosensitive resin composition layer 8 containing a phosphor includes an exposed portion,
Utilizing the difference in the adhesiveness of the unexposed portions, dry development is performed in which only the adhesive unnecessary portions of the photosensitive resin composition layer 8 containing the phosphor (C) together with the mediating layer (B) are peeled off. You can also.

When the photosensitive resin composition layer 8 containing the phosphor (C) remains on the protrusions as shown in FIG. 5, this can be completely removed by polishing or the like. . Alternatively, instead of the polishing, an adhesive tape may be adhered to the unnecessary portion and then peeled off to physically remove only the unnecessary portion.

[(V) Step of Baking the Pattern to Form a Phosphor Pattern] FIG. 4 (VI) shows a state in which the phosphor pattern has been formed after baking off and removing organic substances from the pattern. . In FIG. 4 (VI), reference numeral 12 denotes a phosphor pattern. The firing temperature at this time is preferably from 350 to 800 ° C.,
More preferably, the temperature is set 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 the method (I) according to the present invention is advantageous in that the number of steps can be reduced.
After repeating the steps of (IV) for each color to form a multicolor pattern composed of a photosensitive resin composition layer containing a phosphor that emits red, green, and blue (color order is arbitrary),
It is preferable to perform the step (V) to form a multicolor phosphor pattern.

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

The back plate for a plasma display panel of the present invention is provided with the fluorescent pattern obtained as described above on a substrate for a plasma display panel. The back plate for a plasma display panel will be described below with reference to FIG. FIG. 8 is a schematic view showing an example of a plasma display panel (PDP). In FIG. 8, 1 is a substrate, 2 is a barrier rib, 4 is a stripe-shaped discharge space, 12 is a phosphor pattern, and 13 is an address. Electrodes, 14 a protective film, 15 a dielectric layer, 16
Is a display electrode and 17 is a front plate substrate. In FIG. 8, the lower part including the substrate 1, the barrier ribs 2, the phosphor pattern 12, the dielectric layer 15, and the address electrodes 13 is a PDP.
The upper portion including the protective film 14, the dielectric layer 15, the display electrode 16, and the front plate substrate 17 is a PDP front plate. PDPs can be classified into AC (AC) PDPs, DC (DC) PDPs, and the like according to the voltage application method. The schematic diagram of FIG. 8 shown as an example is an AC PDP.

The method for producing a photosensitive element and a phosphor pattern according to the present invention can be applied to a self-luminous display such as a field emission display (FED) and an electroluminescence display (ELD).

[0064]

The present invention will be described below with reference to examples. Production Example 1 [Preparation of Removable Embedding Layer Solution (a-1)] Table 1
Are mixed with each other, and a solution (a
-1) was prepared.

[0065]

[Table 1]

Production Example 2 [Preparation of Film-Providing Polymer (a) Solution] A solvent mixture shown in Table 2 was charged into a flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer. The temperature was raised to 80 ° C. in a nitrogen gas atmosphere, and a mixed solution of the materials shown in Table 2 was uniformly dropped over 4 hours while maintaining the reaction temperature at 80 ° C. ± 2 ° C. After dropping the mixed solution, 80 ° C ± 2
Stirring was continued for 6 hours at 80 ° C., and the weight average molecular weight was 80,00.
A solution of the polymer (a) (solid content: 45.5% by weight) having an acid value of 130 mgKOH / g was obtained.

[0067]

[Table 2]

Production Example 3 [Preparation of Solution for Intermediate Layer (b-1)]
The solution was mixed and dissolved to prepare a solution (b-1) for the mediating layer.

[0069]

[Table 3]

Production Example 4 [Preparation of Intermediate Layer Solution (b-2)]
The solution was mixed and dissolved to prepare a solution (b-2) for the mediating layer.

[0071]

[Table 4]

Production Example 5 [Solution for Photosensitive Resin Composition Layer Containing Phosphor (c-
1) Production of the materials shown in Table 5 using a bead mill
After mixing for 5 minutes, a solution (c-1) for a photosensitive resin composition layer containing a phosphor was prepared.

[0073]

[Table 5]

Production Example 6 [Solution for Photosensitive Resin Composition Layer Containing Phosphor (c-
2) Production] The materials shown in Table 6 were converted into 1 using a bead mill.
The mixture was mixed for 5 minutes to prepare a photosensitive resin composition layer solution (c-2) containing a phosphor.

[0075]

[Table 6]

Production Example 7 [Solution for Photosensitive Resin Composition Layer Containing Phosphor (c-
Production of 3)] The materials shown in Table 7 were converted into 1 using a bead mill.
After mixing for 5 minutes, a solution (c-3) for a photosensitive resin composition layer containing a phosphor was prepared.

[0077]

[Table 7]

Example 1 [Preparation of photosensitive element (i)] On a polyethylene terephthalate film (first support film) having a thickness of 50 μm, an ethylene-6% by weight ethyl acrylate copolymer was melt-extruded and applied. A layer having a thickness of 30 μm was formed by a process. Next, the releasable burying layer solution (a-1) obtained in Production Example 1 was uniformly applied on this layer.
The solvent was removed by drying with a hot air convection dryer at 0 ° C. for 10 minutes to form a (A) peelable embedded layer having a thickness of 65 μm. Next, on this (A) peelable embedded layer,
The intermediary layer solution (b-1) obtained in Production Example 3 was uniformly applied, dried with a hot air convection dryer at 110 ° C. for 10 minutes to remove the solvent, and a 10 μm thick (B) intermediate layer was formed. Formed.

On the other hand, in the same manner as on the first support film, a 30 μm thick polyethylene terephthalate film (second support film) having a thickness of 50 μm was formed.
To form a layer of an ethylene-6% by weight ethyl acrylate copolymer, and then uniformly apply the photosensitive resin composition layer solution (c-1) containing the phosphor obtained in Production Example 4 on the layer. , 11
The solvent was removed by drying with a hot air convection dryer at 0 ° C. for 10 minutes to form a 40 μm-thick photosensitive resin composition layer containing the phosphor (C). Next, using a laminating roll (lamination), the (B) mediating layer on the first support film and the (C) phosphor-containing photosensitive resin composition layer on the second support film face each other. The temperature was 20 ° C, the laminating speed was 0.5 m / min, and the pressing pressure was 1.2 × 10 ³ N / linear pressure.
m) Laminating and peeling off the second support film to produce photosensitive element (i).

Example 2 [Preparation of photosensitive element (ii)] In the same manner as in Example 1, a 30 μm-thick ethylene-6% film was formed on a 50 μm-thick polyethylene terephthalate film (first support film). An ethyl acrylate copolymer layer, a 65 μm thick (A) peelable buried layer thereon, and a 10 μm thick (B) mediating layer thereon were formed. On the other hand, Example 1
In the same manner as in the above, a 30 μm thick polyethylene terephthalate film (second support film) having a thickness of 50 μm
A layer of a 6 μm ethylene-6% ethyl acrylate copolymer was formed, and the photosensitive resin composition layer solution (c-2) containing the phosphor obtained in Production Example 5 was uniformly applied thereon. , 11
The solvent was removed by drying with a hot air convection dryer at 0 ° C. for 10 minutes to form a 40 μm-thick photosensitive resin composition layer containing the phosphor (C). Next, using a laminating roll (lamination), the (B) mediating layer on the first support film and the (C) phosphor-containing photosensitive resin composition layer on the second support film face each other. The temperature was 20 ° C, the laminating speed was 0.5 m / min, and the pressing pressure was 1.2 × 10 ³ N / linear pressure.
m) Laminating and peeling off the second support film to produce photosensitive element (ii).

Example 3 [Preparation of photosensitive element (iii)] In the same manner as in Example 1, a polyethylene terephthalate film (first support film) having a thickness of 50 µm was coated with 30 µm of ethylene-6 weight by weight. % Ethyl acrylate copolymer layer, a 65 μm-thick (A) peelable burying layer, and a 10 μm-thick layer on the intermediate layer solution (b-2) obtained in Production Example 4 (B) of the intermediate layer was formed. On the other hand, Example 1
In the same manner as in the above, a 30 μm thick polyethylene terephthalate film (second support film) having a thickness of 50 μm
A layer of a 6 μm ethylene-6% ethyl acrylate copolymer was formed, and a solution (c-3) for a photosensitive resin composition layer containing the phosphor obtained in Production Example 6 was uniformly applied thereon. , 11
The solvent was removed by drying with a hot air convection dryer at 0 ° C. for 10 minutes to form a 40 μm-thick photosensitive resin composition layer containing the phosphor (C). Next, using a laminating roll (lamination), the (B) mediating layer on the first support film and the (C) phosphor-containing photosensitive resin composition layer on the second support film face each other. The temperature was 20 ° C, the laminating speed was 0.5 m / min, and the pressing pressure was 1.2 × 10 ³ N / linear pressure.
m) Laminating and peeling off the second support film to produce photosensitive element (iii).

[Evaluation of Photosensitive Element] Examples 1 to 3
The photosensitive element prepared in the above was a photosensitive element having good laminated structure stability, and had a form that could be used for subsequent lamination on an uneven PDP substrate.

Comparative Example 1 An ethylene-6% by weight ethyl acrylate copolymer was melt-extruded onto a 50 μm-thick polyethylene terephthalate film (first support film) by melt extrusion coating.
A layer having a thickness of 30 μm was formed. Next, the solution (a-1) for the peelable embedded layer obtained in Production Example 1 was uniformly applied on this layer, and dried with a hot air convection dryer at 110 ° C. for 10 minutes to remove the solvent. Then, a (A) peelable embedded layer having a thickness of 65 μm was formed.

On the other hand, in the same manner as on the first support film, a 30 μm thick polyethylene terephthalate film (second support film) having a thickness of 50 μm was used.
To form a layer of an ethylene-6% by weight ethyl acrylate copolymer, and then uniformly apply the photosensitive resin composition layer solution (c-1) containing the phosphor obtained in Production Example 4 on the layer. , 11
The solvent was removed by drying with a hot air convection dryer at 0 ° C. for 10 minutes to form a 40 μm-thick photosensitive resin composition layer containing the phosphor (C). Next, a laminating roll is used so that (A) the peelable embedded layer on the first support film and (C) the photosensitive resin composition layer containing the phosphor on the second support film face each other. (Laminating temperature is 20
° C, lamination speed: 0.5 m / min, pressure pressure: 1.2 × 10 ³ N / m at linear pressure). Attempt to peel off and remove second support film. The film alone cannot be peeled off favorably, and peels off between the (A) peelable embedding layer and the (C) phosphor-containing photosensitive resin composition layer that have been bonded together. The photosensitive element could not be produced favorably.

Example 4 The (C) phosphor was formed on the side on which the barrier ribs of the PDP substrate having irregularities (striped barrier ribs, opening width between barrier ribs 150 μm, barrier rib width 70 μm, barrier rib height 150 μm) were formed. The photosensitive element (i) obtained in Example 1 was placed on the first support film by a laminator (at a laminating temperature of 120 ° C. and a laminating speed of 0.1 mm) such that the photosensitive resin composition layer containing 5m / min, pressure pressure is 9.8 × 10 ³ N / m in linear pressure)
The laminate was laminated, and (C) a photosensitive resin composition layer containing a phosphor, (B) an intermediate layer, and (A) a releasable embedding layer were embedded in the inner surface of the recess. Subsequently, (A) the first support film was peeled off together with the peelable embedded layer. The obtained substrate was cut in a direction perpendicular to the stripe direction, and the cut surface was observed with an electron microscope to confirm the phosphor layer forming properties. As a result, a uniform and good phosphor layer was formed. I knew it was there.

Example 5 On the side where the barrier ribs of the PDP substrate having irregularities (striped barrier ribs, opening width between barrier ribs 150 μm, barrier rib width 70 μm, barrier rib height 150 μm) were formed, (C) phosphor The photosensitive element (ii) obtained in Example 2 was placed on the first support film by a laminator (at a laminating temperature of 120 ° C. and a laminating speed of 0.2 ° C.) so that the photosensitive resin composition layer containing 5m / min, pressure pressure is 9.8 × 10 ³ N / m in linear pressure)
The layers were laminated, and the photosensitive resin composition layer containing the phosphor (C), the mediating layer (B), and the releasable burying layer (A) were embedded in the inner surface of the concave portion. Subsequently, (A) the first support film was peeled off together with the peelable embedded layer. The obtained substrate was cut in a direction perpendicular to the stripe direction, and the cut surface was observed with an electron microscope to confirm the phosphor layer forming properties. As a result, a uniform and good phosphor layer was formed. I knew it was there.

Example 6 On the side where the barrier ribs of the PDP substrate having irregularities (striped barrier ribs, opening width between barrier ribs 150 μm, barrier rib width 70 μm, barrier rib height 150 μm) were formed, (C) phosphor The photosensitive element (iii) obtained in Example 3 was placed on the first support film by a laminator (lamination temperature: 120 ° C., lamination speed: 0.1 mm) such that the photosensitive resin composition layer containing 5m / min., Compression pressure is 9.8 × 10 ³ N / in line pressure
m) The layers were laminated, and the photosensitive resin composition layer containing the phosphor (C), the mediating layer (B), and the peelable embedded layer (A) were embedded in the inner surface of the concave portion. Subsequently, (A) the first support film was peeled off together with the peelable embedded layer. The obtained substrate is cut in a direction perpendicular to the stripe direction,
The cut surface was observed with an electron microscope to confirm the phosphor layer forming properties. As a result, it was found that a uniform and good phosphor layer was formed.

Example 7 [Production of Red Phosphor Pattern] [(I) Photosensitive element (i) on substrate having irregularities
And (C) laminating the photosensitive resin composition layer containing the phosphor so as to be in contact with the substrate] in the same manner as in Example 4, using the photosensitive element (i) to apply a red phosphor to the substrate. The contained photosensitive resin composition layer, (B) the mediating layer, and (A) the peelable embedded layer were laminated. [(II) (A) Step of Removing Removable Embedding Layer and First Support Film] Next, the first support film was peeled off together with (A) the releasable embedded layer. [(III) (C) Step of irradiating actinic ray imagewise on the photosensitive resin composition layer containing the phosphor] (B) A test photomask is brought into close contact with the mediating layer, and Oak Manufacturing Co., Ltd. Made H
An actinic ray was imagewise irradiated at 500 mJ / cm ² using an MW-590 type exposure machine.

[(IV) The photosensitive resin composition layer containing the phosphor (C), which has been image-irradiated with actinic rays by development, is selectively removed from the photosensitive resin composition containing the phosphor. Step of forming unnecessary pattern Step of removing unnecessary portion by development] Then, after irradiating with actinic rays, leave at room temperature for 1 hour, and then use 30% aqueous 1% sodium carbonate solution.
Spray development at 120 ° C. for 120 seconds to selectively remove the (C) phosphor-containing photosensitive resin composition layer together with the (B) mediating layer to form a pattern comprising the phosphor-containing photosensitive resin composition did. After development, dried at 80 ° C. for 10 minutes,
Using a Toshiba UV irradiator manufactured by Toshiba Electric Materials Co., Ltd., 3 J / cm
Irradiation with ultraviolet light of No. ² was performed, and heating was further performed in a dryer at 150 ° C. for 1 hour. [(V) Step of Baking the Pattern to Form a Phosphor Pattern] Then, heat treatment (baking) is performed at 500 ° C. for 30 minutes to remove unnecessary resin components, and the surface of the concave portion of the PDP substrate is removed. To form a red phosphor pattern. The cross section of the obtained red phosphor pattern was observed by a stereoscopic microscope and an electron microscope, and the formation state of the red phosphor pattern was evaluated. As a result, the red phosphor layer was formed on the surface of the concave portion of the PDP substrate (the barrier rib wall surface and the substrate). ) Was uniformly formed.

Example 8 [Preparation of Blue Phosphor Pattern] [(I) Photosensitive element (ii) on substrate having irregularities
And (C) laminating the photosensitive resin composition layer containing the phosphor so that the layer is in contact with the substrate] In the same manner as in Example 4, the blue phosphor is applied to the substrate using the photosensitive element (ii). The contained photosensitive resin composition layer, (B) the mediating layer, and (A) the peelable embedded layer were laminated. [(II) (A) Step of Removing Removable Embedding Layer and First Support Film] Next, the first support film was peeled off together with (A) the releasable embedded layer. [(III) (C) Step of irradiating actinic ray imagewise on the photosensitive resin composition layer containing the phosphor] (B) A test photomask is brought into close contact with the mediating layer, and Oak Manufacturing Co., Ltd. Made H
An actinic ray was imagewise irradiated at 500 mJ / cm ² using an MW-590 type exposure machine.

[(IV) The photosensitive resin composition layer containing the phosphor (C), which has been image-irradiated with actinic rays by development, is selectively removed together with the mediating layer (B) to contain the phosphor. Step of forming a pattern composed of a photosensitive resin composition]
Then, after irradiating with actinic light, leave at room temperature for 1 hour
12% at 30 ° C. using 1% by weight aqueous sodium carbonate solution.
Spray development was performed for 0 second, and the photosensitive resin composition layer containing the phosphor (C) was selectively removed together with the mediating layer (B) to form a pattern composed of the photosensitive resin composition containing the phosphor. After development, dry at 80 ° C for 10 minutes.
Ultraviolet irradiation of 3 J / cm ² was performed using a Toshiba ultraviolet irradiation apparatus manufactured by Co., Ltd., and further heated in a dryer at 150 ° C. for 1 hour. [(V) Step of Baking the Pattern to Form a Phosphor Pattern] Then, heat treatment (baking) is performed at 500 ° C. for 30 minutes to remove unnecessary resin components, and the surface of the concave portion of the PDP substrate is removed. Was formed with a blue phosphor pattern. The cross section of the obtained blue phosphor pattern was observed with a stereoscopic microscope and an electron microscope, and the formation state of the blue phosphor pattern was evaluated. As a result, the blue phosphor layer was formed on the surface of the concave portion of the PDP substrate (the barrier rib wall surface and the substrate). ) Was uniformly formed.

Example 9 [Production of green phosphor pattern] [(I) Photosensitive element (ii)
laminating i) with (C) the photosensitive resin composition layer containing the phosphor in contact with the substrate] in the same manner as in Example 4, using the photosensitive element (iii) to obtain green fluorescent light on the substrate. The photosensitive resin composition layer containing the body, (B) the mediating layer, and (A) the peelable embedded layer were laminated. [(II) (A) Step of Removing Removable Embedding Layer and First Support Film] Next, the first support film was peeled off together with (A) the releasable embedded layer. [(III) (C) Step of irradiating actinic ray imagewise on the photosensitive resin composition layer containing the phosphor] (B) A test photomask is brought into close contact with the mediating layer, and Oak Manufacturing Co., Ltd. Made H
An actinic ray was imagewise irradiated at 500 mJ / cm ² using an MW-590 type exposure machine.

[(IV) The photosensitive resin composition layer containing the phosphor (C), which has been imagewise irradiated with actinic rays by development, is selectively removed from the photosensitive resin composition containing the phosphor. Step of Forming a Pattern] Then, after irradiating with actinic rays, the mixture is left at room temperature for 1 hour, and then spray-developed at 30 ° C. for 120 seconds using a 1% by weight aqueous sodium carbonate solution,
(C) The photosensitive resin composition layer containing the phosphor was selectively removed together with the mediating layer (B) to form a pattern comprising the photosensitive resin composition containing the phosphor. After development, 80
At 10 ° C. for 10 minutes, using a Toshiba Denshi Co., Ltd. Toshiba ultraviolet irradiation device, 3 J / cm ² UV irradiation, and further,
Heat in oven at 150 ° C. for 1 hour. [(V) Step of Baking the Pattern to Form a Phosphor Pattern] Then, heat treatment (baking) is performed at 500 ° C. for 30 minutes to remove unnecessary resin components, and the surface of the concave portion of the PDP substrate is removed. To form a green phosphor pattern. The cross section of the obtained green phosphor pattern was observed with a stereoscopic microscope and an electron microscope, and the state of formation of the green phosphor pattern was evaluated. As a result, the green phosphor layer was formed on the surface of the concave portion of the PDP substrate (the barrier rib wall surface and the substrate). ) Was uniformly formed.

From the above results, a good phosphor pattern can be produced by producing a phosphor pattern using the photosensitive element of the present invention.

Embodiment 10 [Formation of Three-Color Pattern] (I) to (I) in Embodiment 7
Using the substrate obtained by performing the step V) on which the photosensitive resin composition layer containing the phosphor that emits the first color red was formed, (I) to (IV) of Example 8 were used. The same steps were performed to form a photosensitive resin composition layer containing a phosphor that emits the second color blue, and then (I) to (9) of Example 9
By performing the same steps as in (IV), a photosensitive resin composition layer containing a phosphor emitting a third color green was formed to form a multicolor pattern. Next, the step (V) in Example 7 was performed using the obtained multicolored pattern, thereby producing a PDP back plate on which a multicolored phosphor pattern was formed. The cross section of the obtained multicolor phosphor pattern was observed by a stereoscopic microscope and an electron microscope, and as a result of evaluating the state of formation of the multicolor phosphor pattern, the multicolor phosphor pattern emitting red, blue and green was It was confirmed that it was formed uniformly on the surface of the concave portion of the back plate for PDP (the barrier rib wall surface and the substrate).

[0096]

According to the first aspect of the present invention, the photosensitive element has a laminating property of each layer and an embedding property in a concave portion of a substrate having irregularities such as a PDP substrate. That can form a highly precise and uniform phosphor pattern with good workability in the concave portion (corresponding to the discharge space) corresponding to the discharge space to be formed (formability of the photosensitive resin composition layer containing the phosphor). It is. The method for manufacturing a photosensitive element according to the second aspect is excellent in workability and stability.

The method of manufacturing a phosphor pattern according to the third aspect of the present invention is directed to a method of embedding a concave / convex substrate such as a PDP substrate into a concave portion (for a PDP substrate, a discharge space composed of rib wall surfaces and a substrate surface). In this case, the phosphor resin-containing photosensitive resin composition layer is excellent in the concave portions (corresponding to the discharge space) corresponding to the above, and a phosphor pattern having a uniform shape can be formed with high precision. The manufacturing method of the phosphor pattern according to the fourth aspect is excellent in workability and environmental safety in addition to the effect of the third aspect. The phosphor pattern according to the fifth aspect has a uniform shape with high accuracy and excellent luminance. A back panel for a plasma display panel according to a sixth aspect is provided with a phosphor pattern having high accuracy, a uniform shape, and excellent brightness.

[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 shows a method for producing a phosphor pattern of the present invention.
(I) This is an example after the end of the process.

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.

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

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Substrate 2 ... Barrier rib 3 ... Grid-like discharge space 4 ... Stripe-like discharge space 5 ... First support film 6 ... Peelable buried layer 7 ... Intermediate layer 8 ... Phosphor-containing photosensitive resin composition layer 8 ': Photosensitive resin composition layer containing phosphor after photo-curing 8'a: First color pattern 8'b: Second color pattern 8'c: Third color pattern 9: Pressure roll 10: Photomask DESCRIPTION OF SYMBOLS 11 ... Active light 12 ... Phosphor pattern 12a ... Phosphor pattern of the first color 12b ... Phosphor pattern of the second color 12c ... Phosphor pattern of the third color 13 ... Electrode for address 14 ... Protective film 15 ... Dielectric layer 16 ... Display Electrode 17… Front plate substrate

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI H01J 11/02 H01J 11/02 B 17/04 17/04 (72) Inventor Naoki Kimura 4-3-1 Higashicho, Hitachi City, Hitachi, Ibaraki, Japan No. Within Hitachi Chemical Co., Ltd.Ibaraki Research Laboratories (72) Inventor Yoshiyuki Horibe 4-13-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. 13-1 Citizen, Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd. (72) Inventor Mariko Shimamura 4-3-1-1, Higashicho, Hitachi City, Ibaraki Pref., Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd.

Claims (6)

[Claims] 1. A first support film, comprising (A) a releasable buried layer, (B) an intermediate layer thereon, and (C) a phosphor thereon. A photosensitive element having a photosensitive resin composition layer. 2. A first element having (A) a releasable embedded layer on a first support film, and further having (B) an intermediate layer formed thereon, and a second support. A second element comprising (C) a phosphor-containing photosensitive resin composition layer on a film is provided by (B) an intermediate layer and (C)
2. The method for producing a photosensitive element according to claim 1, wherein the second support film is removed by peeling off the photosensitive resin composition layer containing the phosphor so that the layers face each other. 3. (I) a step of laminating the photosensitive element according to claim 1 on a substrate having irregularities so that the photosensitive resin composition layer containing the phosphor (C) is in contact with the substrate; II) (A) a step of removing the peelable embedding layer and the first support film, (III) (C) a step of imagewise irradiating the photosensitive resin composition layer containing the phosphor with actinic rays, (IV) A pattern formed of the phosphor-containing photosensitive resin composition is formed by selectively removing the (C) phosphor-containing photosensitive resin composition layer imagewise irradiated with actinic rays by development. And (V) firing the pattern to form a phosphor pattern. 4. Each of the steps (I) to (IV) is repeated for each photosensitive element having a photosensitive resin composition layer containing a phosphor that emits red, green and blue, respectively. After forming a multicolor pattern composed of a photosensitive resin composition containing a phosphor that emits green and blue, (V)
4. The method for producing a phosphor pattern according to claim 3, wherein the step (b) is performed to form a multicolor phosphor pattern. 5. A phosphor pattern produced by the method for producing a phosphor pattern according to claim 3. 6. A back plate for a plasma display panel, comprising the phosphor pattern according to claim 5 on a substrate for a plasma display panel.