JPH11273563A - Method for forming phosphor pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for efficiently and evenly forming phosphor patterns in side walls and bottom parts of partition walls (cells). SOLUTION: This method for forming phosphor patterns in partition walls (cells) of a substrate for a fluorescent display is carried out by forming a resin composition layer (A) containing (a) acrylic polymer with glass transition temperature (Tg) at 30 deg.C or higher, (b) polyhydric alcohol, and (c) phosphors and a photosensitive resin composition (B) in the partition walls (cells), and then exposing, developing, and baking the layers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a phosphor pattern in a partition (cell) at the time of manufacturing a phosphor display device such as a plasma display panel (PDP).

[0002]

2. Description of the Related Art Recently, various flat panel display panels have been actively developed. Among them, PDPs have attracted attention. From display screens of laptop personal computers, various electronic bulletin boards, and so-called "wall mounted televisions". Its use is expanding. A phosphor for display is sealed (fixed) in the cell of the display panel of the PDP, and the phosphor emits color by ultraviolet rays generated by the sealing gas in the cell due to an applied voltage.

As a method of forming such a phosphor pattern, a liquid photoresist in which phosphors of respective colors are dispersed has been used, and in order to improve such a forming method, the present applicant has proposed such a liquid photoresist. Instead of
Proposal of a dry film resist (photoresist film) containing a phosphor (Japanese Patent Laid-Open No. Hei 6-273925), and an acrylic resin layer and a phosphor-containing photosensitive resin composition in order to improve the fixing efficiency of the phosphor. A pattern formation method using a layer stack (Japanese Patent Application Laid-Open No. 9-69339) has been proposed.

Further, in order to obtain a phosphor pattern having a uniform shape with high accuracy, a photosensitive thermoplastic resin layer is heated and pressed on the photosensitive resin composition layer containing the phosphor, and exposed and developed. And a baking method (Japanese Patent Application Laid-Open No. 9-199027), and a photosensitive resin having a photosensitive thermoplastic resin layer on a support film and a phosphor-containing photosensitive resin composition layer thereon. An element and a method in which the photosensitive element is heated and pressed so that a photosensitive resin composition layer containing a phosphor is in contact with a PDP substrate, and is exposed, developed, and fired (JP-A-9-199030). Proposed.

[0005]

However, with respect to the photoresist film described in JP-A-6-273925, sufficient study has been made on the filling properties of the phosphor into the partition walls (cells). Regarding the technique disclosed in Japanese Patent Application Laid-Open No. 9-69339 in consideration of this point, the filling amount of the phosphor in the partition can be ensured, but the phosphor-containing acrylic resin layer is provided after the phosphor-containing resin layer is provided. In order to laminate the photosensitive resin composition layer, there is still room for improvement in that the phosphor is uniformly and efficiently fixed to the side walls and bottom surfaces of the partition walls (cells) (embedding properties).

In the techniques described in JP-A-9-199027 and JP-A-9-199030, the embedding property is relatively good because the phosphor-containing layer is provided on the partition wall side. Since the phosphor-containing layer is provided with photopolymerizability, there is a high possibility that the pattern will be lost during firing, and further improvement is desired. In the present invention, in such a background, in order to make the phosphor filled in the partition (cell) efficiently emit light, the sidewall or the bottom surface of the partition (cell) is deficient during firing as described above. The purpose of the present invention is to form a uniform phosphor pattern. Furthermore, if such a phosphor pattern is formed, an economical secondary effect that the amount of phosphor used can be reduced can be expected.

[0007]

In view of the above circumstances, the present inventors have conducted intensive studies and as a result, have found that when forming a phosphor pattern in a partition (cell) of a fluorescent display substrate, The glass transition temperature (Tg) in the partition (cell)
Resin composition (A) comprising acrylic polymer (a), polyhydric alcohol (b) and phosphor (c) having a temperature of 30 ° C. or higher
After providing a layer and a photosensitive resin composition (B) layer, exposure,
The present inventors have found that a method of forming a phosphor pattern by performing development and baking sufficiently follows the side wall surface and the bottom surface of a partition (cell) (excellent embedding property) to efficiently form a phosphor pattern and completes the present invention. I came to. In the present invention, it is preferable that after the resin composition (A) layer is provided in the partition (cell), the photosensitive resin composition (B) layer is subsequently provided.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
As the resin composition (A) layer used in the present invention, a layer composed of a resin composition (A) composed of an acrylic polymer (a), a polyhydric alcohol (b) and a phosphor (c) is used. The acrylic polymer (a) has a glass transition temperature (Tg) of 30 ° C. or higher, preferably 40 to 20 ° C.
0 ° C., more preferably 45 to 175 ° C., without any particular limitation, containing (meth) acrylate as a main component,
If necessary, an acrylic copolymer obtained by copolymerizing an ethylenically unsaturated carboxylic acid or another copolymerizable monomer is used. Also, an acetoacetyl group-containing acrylic copolymer can be used. The glass transition temperature (Tg) is 3
If the temperature is lower than 0 ° C., the fluidity increases and the storage stability decreases.

Here, (meth) acrylate includes methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Examples thereof include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and glycidyl (meth) acrylate.

As the ethylenically unsaturated carboxylic acid, monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and the like are preferably used. In addition, dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, and anhydrides thereof are also used. Products and half esters can also be used. Of these, acrylic acid and methacrylic acid are particularly preferred. Examples of other copolymerizable monomers include acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, and alkyl vinyl ether.

Among the above acrylic polymers (a), in the present invention, the acrylic polymer (a) has a weight average molecular weight of 10,000 to 300,000 and an acid value of 80 to 300.
Preferably it is 250 mg KOH / g. The particularly preferred weight average molecular weight of the acrylic polymer (a) is 3
000 to 200,000, and a particularly preferred acid value is 9
5 to 220 mgKOH / g. If the weight-average molecular weight is less than 10,000, the film retainability will be insufficient, and if it exceeds 300,000, the resolution will be insufficient due to a decrease in developability, which is not preferable. The acid value is 80mgK
If it is less than OH / g, the resolving power will be insufficient due to a decrease in developability, and if it exceeds 250 mgKOH / g, the developer resistance will decrease, which is not preferable.

The polyhydric alcohol (b) used in the present invention
Is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, and compounds represented by the following general formula (I). H- (O-CH ₂ CHR ₁ ) _n -O- (C ₆
H ₄ ) -R _2- (C ₆ H ₄ ) -O- (CHR ₁ -CH ₂ O) _m -H ... (I) (where R ₁ is a hydrogen or methyl group, and R ₂ is -CH _2- , -C (C
H ₃ ) ₂ — or S, where n and m are positive integers and n
+ M is 2 to 60. In the present invention, in particular, the polyhydric alcohol (b) has a viscosity at 20 ° C. of 50 mPa.
Sec or more, and the viscosity is 50
If it is less than mPa · sec, migration may occur during storage and separation may occur, which is not preferable.

The amount of the polyhydric alcohol (b) is preferably 50 to 300 parts by weight, more preferably 100 to 250 parts by weight, per 100 parts by weight of the acrylic polymer (a). If the amount is less than 50 parts by weight, the flexibility is lowered. If the amount is more than 300 parts by weight, the storage stability such as cold flow and aggregation of the phosphor is lowered, which is not preferable.

Further, the phosphor (c) used in the present invention is not particularly limited, but is preferably a phosphor obtained by using a rare earth oxyhalide or the like as a host and activating the host with an activator. As Y ₂ O ₃ : E
u, YVO ₄ : Eu, (Y, Gd) BO ₃ : Eu (more than red), BaAl ₁₂ O ₁₉ : Mn, Zn ₂ SiO ₄ : Mn, L
aPO ₄ : Tb (green), BaMgAl ₁₄ O ₂₃ : E
u, BaMgAl ₁₆ O ₂₇ : Eu (above blue) and the like, and other phosphors include Y ₂ O ₃ S: Eu, γ-Z
n ₃ (PO ₄ ) ₂ : Mn, (ZnCd) S: Ag + In ₂ O
₃ (red above), ZnS: Cu, Al, ZnS: Au,
Cu, Al, (ZnCd) S: Cu, Al, Zn ₂ Si
O ₄ : Mn, As, Y ₃ Al ₅ O ₁₂ : Ce, Gd ₂ O ₂ S:
Tb, Y ₃ Al ₅ O ₁₂ : Tb, ZnO: Zn (green or more), ZnS: Ag + red pigment, Y ₂ SiO ₃ : Ce (blue or more) and the like can also be used.

The blending amount of the phosphor (c) is 100% of the total amount of the acrylic polymer (a) and the polyhydric alcohol (b).
1 to 1500 parts by weight, more preferably 1 to 1 part by weight
Desirably, the amount is 0 to 800 parts by weight. If the amount is less than 1 part by weight, the luminance is insufficient due to the insufficient amount of the phosphor after pattern formation, and if it exceeds 1500 parts by weight, the flexibility is insufficient, which is not preferable. The method for blending the phosphor (c) is not particularly limited, and is a known method, for example, a mixture of the above-mentioned acrylic polymer (a) and polyhydric alcohol (b), or an acrylic polymer (a) or There is a method in which a predetermined amount of the phosphor (c) is added to one or both of the polyhydric alcohols (b) and the mixture is sufficiently stirred to uniformly disperse the phosphor (c).

The photosensitive resin composition (B) layer is not particularly limited as long as it is a resin composition having photosensitivity. However, the base polymer (d), the ethylenically unsaturated compound (e), the photopolymerization initiator (f) ) Is preferable. As the base polymer (d), besides polyester-based resin, polyurethane-based resin, etc., the same (meth) acrylate component as the above-mentioned acrylic polymer (a), and if necessary, ethylenically unsaturated carboxylic acid and other copolymers. An acrylic copolymer obtained by copolymerizing a polymerizable monomer is appropriately used. The base polymer (d) and the acrylic polymer (a) may be the same or different. Among them, the glass transition temperature (Tg) is 30 ° C. or higher, more preferably 45 to 175 ° C., and the weight average molecular weight is 100.
00 to 300,000, preferably 30,000 to 2,000
It is also preferable that the photosensitive resin composition (B) is of a dilute alkali development type. When the photosensitive resin composition (B) is of a dilute alkali development type, the ethylenically unsaturated carboxylic acid is 10 to 40% by weight. It is necessary to copolymerize to a certain degree, and a base polymer having an acid value of 65 to 260 mgKOH / g, preferably 95 to 220 mgKOH / g is suitably used.

As the ethylenically unsaturated compound (e),
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl Glycol di (meta)
Acrylate, 1,6-hexane glycol di (meth)
Acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2,2-bis (4 -(Meth) acryloxydiethoxyphenyl) propane, 2,2-bis- (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3-
(Meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl Examples include polyfunctional monomers such as ether poly (meth) acrylate.

An appropriate amount of a monofunctional monomer may be used in combination with these polyfunctional monomers. Examples of such a monofunctional monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, -Hydroxybutyl (meth) acrylate, 2
-Phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropylphthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) ) Acryloyloxyethyl acid phosphate, half (meth) acrylate of a phthalic acid derivative, N-methylol (meth) acrylamide, and the like.

The amount of the ethylenically unsaturated compound (e) to be added is 2 to 100 parts by weight of the base polymer (d).
It is preferable to select from the range of 0 to 100 parts by weight, preferably 30 to 100 parts by weight. When the amount of the ethylenically unsaturated compound (e) is too small, it causes poor curing and a delay in development speed when the photosensitive resin composition (B) is used, and also causes a decrease in flexibility when the layer is used as a layer. On the other hand, an excessive amount of the ethylenically unsaturated compound (e) is not preferable because it causes a cold flow and, when the photosensitive resin composition (B) is used, lowers the peeling rate of the cured resist.

Examples of the photopolymerization initiator (f) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether,
Benzyl diphenyl disulfide, benzyl dimethyl ketal, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3'-dimethyl-4-methoxybenzophenone, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino ) Benzophenone, 4,4'-diethylaminobenzophenone, pivaloin ethyl ether, 1,1-dichloroacetophenone, pt-butyldichloroacetophenone, 2,2'-bis (o-chlorophenyl) 4
5,4 ', 5'-tetraphenyl-1,2'-biimidazole, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2'
-Diethoxyacetophenone, 2,2'-dichloro-4
Phenoxyacetophenone, phenylglyoxylate, α-hydroxyisobutylphenone, dibenzosparone, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-propanone, 2-methyl- [4
-(Methylthio) phenyl] -2-morpholino-1-
Examples include propanone, tribromophenylsulfone, tribromomethylphenylsulfone, and the like.

The compounding amount of the photopolymerization initiator (f) is the same as that of the base polymer (d) and the ethylenically unsaturated compound (e).
0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, based on 100 parts by weight in total. If the amount is less than 0.1 part by weight, the sensitivity is significantly reduced,
If the amount exceeds 20 parts by weight, plasticity increases and storage stability decreases, which is not preferable.

Further, the resin composition (A) and the photosensitive resin composition (B) containing the above-mentioned phosphor may further include a dye (colored or colored), an adhesion-imparting agent, a plasticizer, an antioxidant,
Additives such as a thermal polymerization inhibitor, a solvent, a surface tension modifier, a stabilizer, a chain transfer agent, an antifoaming agent, and a flame retardant can be appropriately added.

[0023] The resin composition (A) layer having a thickness (h _a)
Although it depends on the content of the phosphor (c) and the structure of the PDP and cannot be stated unconditionally, it is usually preferable to be thinner than the partition wall side height (h ₀ ), and furthermore, such h _a (μm) and h ₀ is preferably ([mu] m) is a _{h a / h 0 = 1 /} 20~15 / 20, in particular _{h a / h 0 = 1 /} 20~10 / 20
Is preferably, according h _a / h ₀ is the phosphor insufficient thickness after firing is less than 1/20, 15/20 conversely
Exceeding the limit undesirably reduces the space at the time of cell discharge.

Thickness (h _b ) of photosensitive resin composition (B) layer
Also depends on the structure of the PDP,
Similarly usually the above h _a, thinner is more preferable than the partition wall side height (h _0), even according h _b a (μm) h ₀ (μ
Preferably m) is _{h b / h 0 = 1 /} 20~15 / 20, preferably in particular _{h b / h 0 = 1 /} 20~10 / 20, according h _b / h ₀ is 1 When the ratio is less than / 20, it is difficult to sufficiently push the resin composition (A) layer into the partition walls (cells).

When a layer is formed using the resin composition (A) containing the phosphor and the photosensitive resin composition (B), the layer can be used as a liquid. In consideration of properties, uniformity of coating thickness, storage stability, followability to partition walls, workability, and the like, it is preferable to form a film in advance, and specifically, the above resin composition (A), The resin composition (B) is coated on a base film surface such as a polyester film, a polypropylene film or a polystyrene film, and then coated with a protective film such as a polyethylene film or a polyvinyl alcohol-based film on the coated surface. It is preferable to use them. Next, a method for forming a phosphor pattern will be specifically described.

(Formation of Resin Composition (A) Layer) Base film (polyester film, polyvinyl alcohol film, nylon film, cellulose film) of a laminate having the above-mentioned phosphor-containing resin composition (A) layer as an intermediate layer Etc.) and the resin composition (A) layer and the protective film and the resin composition (A) layer are compared with each other. The resin composition (A) is pressed into the partition (cell) by using a hot laminator or the like to push the resin composition (A) layer into the PDP substrate on which the partition (cell) is formed in advance. Form a layer.

(Formation of Photosensitive Resin Composition (B) Layer) The film remaining on the surface of the resin composition (A) layer was peeled off, and the photosensitive resin composition (B) layer was laminated thereon as an intermediate layer. The photosensitive resin composition (B) layer is formed by pushing the body into the cell using a hot laminator or the like in the same manner as the above-mentioned layer (A). Here, the resin composition (A) layer / photosensitive resin composition (B) is provided inside the partition walls (cells) of the PDP substrate.
Although mean that two layers of the layers are laminated and filled, the ratio h _a / h _b between the thickness (h _b) of use in this case (A) layer thickness and (h _a) (B) layer, It is preferably 10/90 to 75/25. In addition to the above method, the resin composition (A) layer and the photosensitive resin composition (B) layer are laminated in advance to form a laminate, and the laminate ((A) layer / (B) layer / base) The (A) layer side of the film) is a P on which partition walls (cells) are formed in advance.
The laminate may be pressed into a partition (cell) using a hot laminator or the like attached to a DP substrate.

(Exposure) The photosensitive resin composition (B) is exposed by bringing a pattern mask into close contact therewith. At this time, if necessary, and if the photosensitive resin composition (B) layer has no tackiness, the film on the surface of the photosensitive resin composition (B) layer is peeled off, and then the pattern mask is replaced with the photosensitive resin. Exposure can also be performed by directly contacting the composition (B) layer. Exposure is usually performed by ultraviolet irradiation, and as a light source at that time, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp, or the like is used. After irradiation with ultraviolet rays, heating can be performed as necessary to complete the curing.

(Development) After exposure, the film on the layer of the photosensitive resin composition (B) is peeled off and developed.
Since the photosensitive resin composition (B) layer is a diluted alkali developing type photosensitive resin composition, development after exposure uses a dilute aqueous solution of about 1 to 2% by weight of an alkali such as sodium carbonate or potassium carbonate. Do it. At this time, it is also possible to use a developer such as an organic alkali.

(Firing) The partition (cell) forming substrate after the above treatment is baked at 450 to 550 ° C. to fix the phosphor inside the partition (cell) and form a phosphor pattern. Thus, according to the method of the present invention, a phosphor pattern can be uniformly formed in a partition (cell) without causing a pattern defect at the time of firing.
In order to form DP, the resin composition (A) containing the respective phosphors of red, green and blue and the photosensitive resin composition (B) are used to form the above-mentioned resin composition containing the phosphor. After (A) layer formation) to (development) are repeated, the above three color (R (red), G (green), and B (blue)) phosphors are filled in the cell, and then (firing) is performed. By doing so, it can be manufactured.

[0031]

The present invention will be specifically described below with reference to examples. In the examples, “parts” means on a weight basis unless otherwise specified.

Example 1 A resin composition was prepared using 50 parts of the following acrylic polymer (a), 75 parts of polyhydric alcohol (b), and 65 parts of phosphor (c) (using red, green and blue separately). (A) was adjusted. [Resin composition (A)] Acrylic polymer (a) The copolymerization ratio of methyl methacrylate / n-butyl methacrylate / methacrylic acid is 30/49/21 on a weight basis.
(Glass transition temperature 69 ° C., weight average molecular weight 60000, acid value 137 mg KOH / g) polyhydric alcohol (b) polyethylene glycol (viscosity 170 mPa at 20 ° C. )
· Sec, a weight average molecular weight 600), phosphor (c) (Y, Gd, Eu) BO 3 ( red) (emission wavelength 593nm, 610nm, 626nm, particle size; 2-4 [mu] m, specific gravity; 5.1) (Zn , Mn) ₂ SiO ₄ (green) (emission wavelength 529 nm, particle size: 2 to 6 μm, specific gravity;
2) (Ba, Eu) MgAl ₁₀ O ₁₇ (blue) (Emission wavelength: 451 nm, particle size: 2 to 6 μm, specific gravity;
8)

Further, 60 parts of the following base polymer (d),
The photosensitive resin composition (B) was prepared using 40 parts of the ethylenically unsaturated compound (e) and 10 parts of the photopolymerization initiator (f). [Photosensitive resin composition (B)] base polymer (d) methyl methacrylate / n-butyl methacrylate / 2
A copolymer having a copolymerization ratio of ethylhexyl acrylate / methacrylic acid of 50/15/10/25 by weight (glass transition temperature: 75 ° C., weight average molecular weight: 6,000)
0, acid value 163 mgKOH / g). Ethylenically unsaturated compound (e) tetraethylene glycol dimethacrylate 25 parts trimethylolpropane triacrylate 15 parts photopolymerization initiator (f) benzyl dimethyl ketal

Then, the obtained resin composition (A) was applied on a polyester film having a thickness of 20 μm using an applicator having a gap of 10 mm, left at room temperature for 1 minute and 30 seconds, and then left at 60 ° C. and 90 ° C. And an oven at 110 ° C. for 3 minutes each to prepare a resin composition (A) layer having _a thickness (ha) of 50 μm. (However, no protective film was provided.) In the resin composition (A) layer, one containing one of each of red, green, and blue was prepared. Further, using the photosensitive resin composition (B), a thickness (h _b ) of 7
A 0 μm layer of the photosensitive resin composition (B) was prepared. (However, no protective film was provided.) Using the obtained laminate of the layer (A) and the layer (B), a phosphor pattern was formed in the following manner.

(Formation of Resin Composition (A) Layer and Photosensitive Resin Composition (B) Layer) Partition walls (height (h ₀ ) 120 μm, width 45 μm, slit 180 μm) preheated to an oven at 60 ° C.
m PDP substrate (2 stripe pattern)
00 mm × 200 mm × 2 mm) and the resin composition (A) layer (laminated film) on a laminating roll at a temperature of 12 mm.
0 ° C., roll pressure 3 kg / cm ² , lamination speed 0.5
After laminating under the conditions of m / min, the polyester film was peeled off, and the photosensitive resin composition (B) layer (laminated film) was similarly laminated on the polyester film to form the resin composition (A) layer and the photosensitive resin composition. A product (B) layer was formed.

(Exposure and Development) Next, a pattern is placed on the entire surface of the polyester film on the photosensitive resin composition (B) layer so that the inside of the partition (cell) (other than the upper part of the partition) is exposed. And an exposure machine HMW-
Exposure was performed at 532D with a 3 kw ultrahigh pressure mercury lamp. The exposure was performed using a 21-step stofer step tablet at an exposure giving step 7. After a hold time of 15 minutes after the exposure, development was carried out in a 1% aqueous sodium carbonate solution at 30 ° C. for twice the minimum development time to form a red line. Further, the same operation was performed to form a green line and a blue line.

(Firing) After development, put in a firing furnace,
The temperature was raised to 0 ° C. to burn off the resin components in the resin composition (A) layer and the photosensitive resin composition (B) layer, thereby forming red, green, and blue phosphor patterns.

The obtained partition substrate on which the phosphor pattern was formed had no pattern loss due to firing, and when the cross section of the phosphor pattern was observed with a scanning electron microscope (SEM), the cross section was lower than the upper wall of the cell. The phosphor was efficiently and uniformly formed up to that point.

Example 2 The procedure of Example 1 was repeated, except that the composition of the acrylic polymer in the resin composition (A) was changed as follows.
A phosphor pattern was formed. As in Example 1, the partition substrate on which the obtained phosphor pattern was formed had no pattern loss due to firing, and the phosphor was efficiently and uniformly formed from the top to the bottom of the cell wall. Was. Acrylic polymer (a) The copolymerization ratio of methyl methacrylate / n-butyl methacrylate / methacrylic acid is 50/20/30 by weight.
(Glass transition temperature: 79.6 ° C., weight average molecular weight: 120,000, acid value: 195.3 mg KOH / g)

Example 3 A phosphor pattern was formed in the same manner as in Example 1, except that the polyhydric alcohol (b) in the resin composition (A) was changed to the following compound. As in Example 1, the partition substrate on which the obtained phosphor pattern was formed had no pattern loss due to firing, and the phosphor was efficiently and uniformly formed from the top to the bottom of the cell wall. Was. Polyhydric alcohol (b) a compound represented by the following formula (BA-
10 _{glycol) HO- (CH 2 -CH 2 -O} ) n -C 6 H 4 -C (CH 3) 2 -C 6 H 4 - (O-CH 2 -CH 2) m -OH ( wherein, n , M is a positive number and n + m is 10. (Viscosity at 20 ° C. is 2,600 mPa · sec, weight average molecular weight is 668)

Comparative Example 1 A phosphor pattern was formed in the same manner as in Example 1, except that the polyhydric alcohol (b) in the resin composition (A) was not blended. The partition substrate on which the obtained phosphor pattern was formed could not obtain sufficient fluidity due to lack of flexibility, and could not obtain good results.

Comparative Example 2 A phosphor pattern was formed in the same manner as in Example 1, except that polyethylene glycol dimethacrylate was added as an ethylenically unsaturated compound instead of polyethylene glycol. The partition substrate on which the obtained phosphor pattern was formed had unevenness during firing, and uniform luminance was not obtained.

[0043]

The method for forming a phosphor pattern according to the present invention comprises:
A resin composition (A) layer containing a phosphor (having no photosensitivity) and a photosensitive resin composition (B) layer not containing a phosphor are formed so as to be filled in a partition (cell). For,
It is excellent in embedding into partition walls (cells), has no pattern loss during firing, and can efficiently and uniformly form a phosphor on the side walls and bottom of the partition walls (cells). Very useful for forming applications.

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[Procedure amendment]

[Submission date] February 19, 1999

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction contents]

Examples of the photopolymerization initiator (f) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether,
Benzyl diphenyl disulfide, benzyl dimethyl ketal, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3'-dimethyl-4-methoxybenzophenone, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino ) benzophenone down, pivaloyl in ethyl ether,
1,1-dichloroacetophenone, pt-butyldichloroacetophenone, 2,2'-bis (o-chlorophenyl) 4,5,4 ', 5'-tetraphenyl-1,2'
-Biimidazole, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2'-diethoxyacetophenone, 2,2'-
Dichloro-4-phenoxyacetophenone, phenylglyoxylate, α-hydroxyisobutylphenone,
Dibenzosparone, 1- (4-isopropylphenyl)
-2-hydroxy-2-methyl-1-propanone, 2-
Methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, tribromophenylsulfone, tribromomethylphenylsulfone, and the like.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction contents]

Next, the obtained resin composition (A) was coated on a polyester film having a thickness of 20 μm using an applicator having a gap of 10 mil , left at room temperature for 1 minute and 30 seconds, and then heated at 60 ° C. and 90 ° C. And an oven at 110 ° C. for 3 minutes each to prepare a resin composition (A) layer having _a thickness (ha) of 50 μm. (However, no protective film was provided.) In the resin composition (A) layer, one containing one of each of red, green, and blue was prepared. Further, using the photosensitive resin composition (B), a thickness (h _b ) of 7
A 0 μm layer of the photosensitive resin composition (B) was prepared. (However, no protective film was provided.) Using the obtained laminate of the layer (A) and the layer (B), a phosphor pattern was formed in the following manner.

Claims (7)

[Claims] 1. An acrylic polymer (a) having a glass transition temperature (Tg) of 30 ° C. or more in a partition (cell) for forming a phosphor pattern in a partition (cell) of a fluorescent display substrate. ), A resin composition (A) layer comprising a polyhydric alcohol (b) and a phosphor (c), and a photosensitive resin composition (B) layer, and then exposure, development, and baking are performed. Phosphor pattern forming method. 2. The acrylic polymer (a) having a glass transition temperature (Tg) of 30 ° C. or higher has a weight average molecular weight of 1,000.
0 to 300,000 and an acid value of 80 to 250 mgK
2. The method for forming a phosphor pattern according to claim 1, wherein the ratio is OH / g. 3. The method according to claim 1, wherein the viscosity of the polyhydric alcohol (b) at 20 ° C. is 50 mPa · sec or more. 4. The phosphor (c) in the resin composition (A)
Is 1 to 1500 parts by weight based on 100 parts by weight of the total amount of the acrylic polymer (a) and the polyhydric alcohol (b) having a glass transition temperature (Tg) of 30 ° C. or higher. Item 4. The method for forming a phosphor pattern according to any one of Items 1 to 3. 5. The photosensitive resin composition (B) layer is a photosensitive resin composition layer comprising a base polymer (d), an ethylenically unsaturated compound (e), and a photopolymerization initiator (f). The method for forming a phosphor pattern according to claim 1. 6. The method according to claim 1, wherein a resin composition (A) layer is provided in the partition (cell), and then a photosensitive resin composition (B) layer is provided. A method for forming a phosphor pattern. 7. A method according to claim 1, wherein the phosphor pattern of three colors of R (red), G (green) and B (blue) is formed three times. A method for forming a phosphor pattern.