JP2001216895A - Method of forming fluorescent pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of economically forming a fluorescent pattern which is improved in brightness, while also taking into account of the environmental problem. SOLUTION: This method for forming fluorescent pattern in a barrier plate of a plasma display panel, comprises forming a reflective layer (A) containing inorganic compound (a) selected from alumina, titanium oxide, yttrium oxide, magnesium oxide, calcium oxide, tantalum oxide, silicon oxide, barium oxide and recovered phosphors, and a layer (B), including the phosphor are successively in the barrier plate, and executing exposure, development and baking.

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) of a plasma display panel (PDP) or the like, and more particularly, to an economical method and a method of providing a good luminance in phosphor display. The present invention relates to a method for forming the phosphor pattern shown in FIG.

[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 partition of the display panel of the PDP, and the phosphor emits color by ultraviolet rays generated by a sealing gas in the partition 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. However, for the photoresist film described in Japanese Patent Application Laid-Open No. 6-273925, the filling of the phosphor into the partition walls has been proposed. There have not been enough studies on gender,
In the technology disclosed in Japanese Patent Application Laid-Open No. 9-69339 in consideration of this point, although the filling amount of the phosphor in the partition can be ensured, the phosphor is uniformly and efficiently fixed to the side and bottom surfaces of the partition, and the luminance is efficiently increased. There is still room for improvement in obtaining

For the purpose of improving the brightness, Japanese Patent Application Laid-Open No.
In the technology disclosed in JP-A-293262, it is disclosed in Japanese Patent Application Laid-Open No. 9-120776 that the lower layer on the back side of the discharge space in the phosphor layer has a denser layer structure than the upper layer on the front side. In the technology, it has been proposed to provide a reflection film for reflecting the light emitted by the phosphor layer between the phosphor layer forming surface in the partition and the phosphor layer.

[0005]

However, in the technology disclosed in the above-mentioned publication, although it is recognized to some extent that the luminance of the phosphor is improved, since the phosphor paste is applied to the substrate, the workability and the filling property of the phosphor are reduced. It is inferior, and with the recent advancement of technology, further improvement such as improvement of luminance and filling property of a phosphor is desired. Further, in the method of forming a pattern of the phosphor using a photoresist film, by a developing step performed at the time of forming the pattern of the phosphor,
About 2/3 of the phosphor was wasted, which not only increased the cost, but also left a problem on the environmental impact.

In view of the above, an object of the present invention is to provide a method for forming a phosphor pattern which is economical and environmentally friendly, while improving luminance under such a background. .

[0007]

Means for Solving the Problems However, the present inventors have conducted intensive studies in view of the above circumstances, and as a result, have found that the PDP
In forming a phosphor pattern in the partition walls, an inorganic compound (a) selected from alumina, titanium oxide, yttrium oxide, magnesium oxide, calcium oxide, tantalum oxide, silicon oxide, barium oxide, and a recovered phosphor is formed in the partition walls. After forming a reflective layer (A) comprising the above) and a layer comprising a phosphor-containing layer (B) provided thereon,
The method of forming a phosphor pattern that performs development and baking can improve the luminance, and when the recovered phosphor is selected as the inorganic compound (a), the phosphor that becomes a waste material is reused as the recovered phosphor. It is economical because it can be done, and it is possible to eliminate waste materials and find that it is also environmentally friendly,
The present invention has been completed. Further, by providing the reflective layer (A), the thickness of the phosphor-containing layer (B) can be reduced as compared with the case where the reflective layer (A) is not provided.
The use amount of the phosphor can be reduced, and furthermore, it has an economic effect.

In the present invention, it is preferable that after the reflection layer (A) is provided in the partition wall of the PDP, the phosphor-containing layer (B) is then provided thereon, and the reflection layer (A) is provided. In using the dry film (F1) in which the reflective layer (A) is laminated on a support film (or sheet) and providing the phosphor-containing layer (B), the phosphor-containing layer (B) Or, a dry film (F2) laminated on a sheet) is preferably used. Also, P
A laminate of a reflection layer (A) and a phosphor-containing layer (B) formed in a sheet or film shape in advance in a partition wall of the DP is
It is also preferable to provide the reflective layer (A) with the reflective layer (A) facing the partition.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
As the reflection layer (A) used in the present invention, an inorganic compound (a) selected from a white pigment such as alumina, titanium oxide, yttrium oxide, magnesium oxide, calcium oxide, tantalum oxide, silicon oxide, barium oxide and a recovered phosphor.
And preferably further contains a base polymer (b) and an ethylenically unsaturated compound (c). In particular, it is preferable that the layer is a layer composed of a resin composition in which the inorganic compound (a) is dispersed in a resin composition composed of the base polymer (b) and the ethylenically unsaturated compound (c).

Here, the term “recovered phosphor” as used in the present invention means a phosphor that has been used and recovered once.
For example, using a photoresist film containing a normal phosphor, filling the photoresist film in the partition, exposed, developed when forming a phosphor pattern, developed and recovered in the development step Phosphor contained in the composition, that is, a phosphor whose emission characteristics are deteriorated compared to a normal phosphor, and in the present invention, the recovered phosphor is reused without being discarded. By that
Alumina, titanium oxide, yttrium oxide, magnesium oxide, calcium oxide, tantalum oxide, silicon oxide,
As with white pigments such as barium oxide, the purpose of the present invention is to improve the luminance and to cope with cost and environment. In addition, "phosphor" means a normal unused phosphor with respect to "recovered phosphor".

The fluorescent material is not particularly limited, but is rare.
Earth oxyhalide, etc. as a base, and this base with an activator
Activated ones are preferred, for example with UV-excited phosphors
Then Y_TwoO_Three: Eu, YVO_Four: Eu, (Y, Gd)
BO_Three: Eu (more than red), BaAl₁₂O₁₉: Mn, Z
n_TwoSiO_Four: Mn, LaPO_Four: Tb (green above), B
aMgAl₁₄O_{twenty three}: Eu, BaMgAl₁₆O₂₇: Eu,
BaMgAl_TenO₁₇: Eu (all blue) and the like,
Other phosphors include Y_TwoO_ThreeS: Eu, γ-Zn_Three
(PO_Four)_Two: Mn, (ZnCd) S: Ag + In_TwoO
_Three(Red above), ZnS: Cu, Al, ZnS: Au,
Cu, Al, (ZnCd) S: Cu, Al, Zn_TwoSi
O_Four: Mn, As, Y_ThreeAl_FiveO₁₂: Ce, Gd_TwoO_TwoS:
Tb, Y_ThreeAl_FiveO ₁₂: Tb, ZnO: Zn (more green
Color), ZnS: Ag + red pigment, Y_TwoSiO_Three: Ce (below)
Upper blue) can also be used.

With respect to the content of the inorganic compound (a), when the base polymer (b) and the ethylenically unsaturated compound (c) described below are contained, the base polymer (b) and the ethylenically unsaturated compound ( Total amount of c) 100
The amount is preferably from 1 to 1500 parts by weight, more preferably from 10 to 800 parts by weight, based on parts by weight. If the amount is less than 1 part by weight, the luminance after pattern formation is insufficient, and if it exceeds 1500 parts by weight, flexibility is insufficient, which is not preferable.

As the base polymer (b), acrylic resin, polyester resin, polyurethane resin and the like are used. Among them, (meth) acrylate is a main component, and if necessary, ethylenically unsaturated carboxylic acid is used. And acrylic copolymers obtained by copolymerizing other copolymerizable monomers are important. An acetoacetyl group-containing acrylic copolymer can also be used.

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 and crotonic acid are preferably used, and dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, and anhydrides thereof. Products and half esters can also be used. Of these, acrylic acid and methacrylic acid are particularly preferred. Such an ethylenically unsaturated carboxylic acid is preferably about 15 to 30% by weight (about 100 to 200 mgKOH / g in acid value). Other copolymerizable monomers include acrylamide, methacrylamide, acrylonitrile,
Methacrylonitrile, styrene, α-methylstyrene,
Examples thereof include vinyl acetate and alkyl vinyl ether.

The weight average molecular weight of the base polymer (b) is preferably from 10,000 to 300,000, more preferably from 30,000 to 200,000. If the weight average molecular weight is less than 10,000, the film retainability of the film will be insufficient, and if it exceeds 300,000, the resolving power will be insufficient due to a decrease in developability, which is not preferable.

As the ethylenically unsaturated compound (c),
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 (c) is 2 parts by weight based on 100 parts by weight of the base polymer (b).
It is preferable to select from the range of 0 to 100 parts by weight, preferably 30 to 100 parts by weight. An insufficient amount of the ethylenically unsaturated compound (c) causes poor curing and a delay in the development speed, and
In the case of a layer, the flexibility is lowered, and an excessive amount of the ethylenically unsaturated compound (c) causes a cold flow, which is not preferable.

The method for blending the inorganic compound (a) is not particularly limited, and is a known method, for example, a mixture of the base polymer (b) and the ethylenically unsaturated compound (c) or the base polymer (b). Alternatively, there is a method in which a predetermined amount of the inorganic compound (a) is added to one or both of the ethylenically unsaturated compounds (c), and the mixture is sufficiently stirred to uniformly disperse the inorganic compound (a).

The phosphor-containing layer (B) used in the present invention is not particularly limited as long as it is a layer containing a phosphor.
A polymer containing a base polymer (d), an ethylenically unsaturated compound (e), a photopolymerization initiator (f) and a phosphor (g) is preferable. Particularly, the base polymer (d),
It is preferably a layer of a resin composition in which a phosphor (g) is dispersed in a resin composition comprising an ethylenically unsaturated compound (e) and a photopolymerization initiator (f).

The base polymer (d) is not particularly limited and may be the same as the above-mentioned base polymer (b). The ethylenically unsaturated compound (e) is not particularly limited. The same thing as the said ethylenically unsaturated compound (c) is mentioned. In the practice, the base polymer (b) and the base polymer (d), and the ethylenically unsaturated compound (c) and the ethylenically unsaturated compound (e) may be the same or different. Is also good.

The photopolymerization initiator (f) is not particularly restricted but includes, for example, 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, p
-T-butyldichloroacetophenone, hexaarylimidazole dimer, 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.

The compounding amount of the photopolymerization initiator (f) is the above-mentioned base polymer (d) and the ethylenically unsaturated compound (e).
Is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the total amount of If the amount is less than 0.1 part by weight, the sensitivity is remarkably lowered. If the amount exceeds 20 parts by weight, the plasticity increases and the storage stability decreases, which is not preferable.

The phosphor (g) used in the phosphor-containing layer (B) includes the above-mentioned phosphors. The amount of the phosphor (g) is based on 100 parts by weight of the total amount of the base polymer (d) and the ethylenically unsaturated compound (e).
It is preferably from 1 to 800 parts by weight, more preferably from 10 to 500 parts by weight.

If the amount is less than 1 part by weight, the luminous efficiency will be reduced when emitting light in the case of PDP, and if it exceeds 800 parts by weight, the film-forming property will be reduced, which is not preferable. In addition to the above, the reflective layer (A) and the phosphor-containing layer (B) further include a dye (colored or colored), an adhesion promoter, a plasticizer, an antioxidant, a thermal polymerization inhibitor, a solvent,
Additives such as a surface tension modifier, a stabilizer, a chain transfer agent, an antifoaming agent, and a flame retardant can be appropriately added.

[0027] The thickness of the reflective layer (A) layer (h _a) is alumina, titanium oxide, yttrium oxide, magnesium oxide, calcium oxide, tantalum oxide, silicon oxide, a white pigment such as barium oxide, from recovered phosphor can not be said categorically also varies depending on the structure of the content and PDP inorganic compound (a) chosen, usually thinner is favored over the partition wall side height (h _0), even with such h _a (μm) h
₀ is preferably ([mu] m) is a _{h a / h 0 = 1 /} 20~15 / 20, preferably in particular _{h a / h 0 = 1 /} 20~10 / 20, according h _a / h ₀ If the ratio is less than 1/20, the thickness of the reflective layer after firing will be insufficient, and if it exceeds 15/20, the space at the time of discharge of the cell will decrease, which is not preferable.

The thickness (h _b ) of the phosphor-containing layer (B) is also P
Can not be said categorically also varies depending on the structure of the DP, usually similar to the above h _a, thinner is more preferable than the partition wall side height (h _0), even according h _b a (μm) h ₀ (μm) preferably but 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 1/20 If it is less than 15%, it is difficult to sufficiently push the above-mentioned reflective layer (A) into the partition walls, and if it exceeds 15/20, the patterning properties are undesirably deteriorated. Further, the reflective layer total thickness of the thickness and the phosphor-containing layer (A) (B) (h a + h b) barrier ribs side height also (h ₀₎ preferably thin than. Furthermore, the ratio between the thickness (h _b) of the thickness of the reflective layer _(A) (h _a) and the phosphor-containing layer _{(B) (h a / h} b) is 90/10
It is preferably 25/75.

In forming the reflection layer (A) and the phosphor-containing layer (B), each resin composition can be used as a liquid. However, the dispersion stability of additives, the uniformity of coating thickness, In consideration of storage stability, followability to partition walls, workability, and the like, it is preferable to form a film (or a sheet) in advance. Specifically, each resin composition is made of a polyester film, a polypropylene film, a polystyrene. It is preferable that after coating on a support film surface such as a film, a protective film such as a polyethylene film or a polyvinyl alcohol film is coated on the coated surface and used as a laminate.

Here, the reflective layer (A) is laminated on a support film, and if necessary, a protective film is further laminated on the reflective layer (A) side to obtain a dry film (F1) and a phosphor-containing layer (B). Is laminated on a support film and, if necessary, further laminated on the phosphor-containing layer (B) side is referred to as a dry film (F2).

Next, the method for forming the phosphor pattern of the present invention will be described in particular with regard to the fluorescence using the dry film (F1) comprising the reflective layer (A) and the dry film (F2) comprising the phosphor-containing layer (B). A method for forming a body pattern will be specifically described. However, the present invention is not limited to this. For example, the reflective layer (A) and the phosphor-containing layer (B) may be formed using a paste of each resin composition to form a phosphor pattern. it can.

(Formation of Reflective Layer (A)) The support film (polyester film, polyvinyl alcohol film, nylon film, cellulose film, etc.) of the dry film (F1) using the above-mentioned reflective layer (A) as an intermediate layer and the reflective film The adhesion between the layer (A) and the adhesion between the protective film and the reflective layer (A) are compared, and the lower adhesive film is peeled off to form a partition on the side of the reflective layer (A) in advance. The reflective layer (A) is formed on the PDP substrate by using a hot laminator or the like to push the reflective layer (A) into the partition walls.

(Formation of Phosphor-Containing Layer (B)) The film remaining on the surface of the reflecting layer (A) was peeled off, and a dry film (F) using the phosphor-containing layer (B) as an intermediate layer was peeled from above.
The phosphor-containing layer (B) is formed by pushing 2) into the partition using a hot laminator or the like in the same manner as the layer (A). Here, in the partition of the PDP substrate,
Two layers of the reflection layer (A) / the phosphor-containing layer (B) are stacked and filled.

In addition to the above method, the reflection layer (A) and the phosphor-containing layer (B) are laminated in advance to form a laminate.
The reflective layer (A) side of the laminate ((A) / (B) / support film) is attached to a PDP substrate having partition walls formed in advance,
The laminate may be pushed into the partition using a hot laminator or the like.

(Exposure) Exposure is performed by closely attaching a pattern mask to the phosphor-containing layer (B). At this time, if necessary,
When the phosphor-containing layer (B) has no tackiness, the film on the surface of the phosphor-containing layer (B) may be peeled off, and then the pattern mask may be directly contacted with the phosphor-containing layer (B) for exposure. it can. 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 phosphor-containing layer (B) is peeled off and developed. Since the reflection layer (A) and the phosphor-containing layer (B) are of a dilute alkali developing type, development after exposure is performed using a dilute aqueous solution of about 1 to 2% by weight of an alkali such as sodium carbonate or potassium carbonate. . At this time, it is also possible to use a developer such as an organic alkali.

(Firing) The partition-forming substrate after the above-described treatment is placed in the
Baking is performed at 0 to 550 ° C., and an inorganic compound (a) selected from white pigments such as alumina, titanium oxide, yttrium oxide, magnesium oxide, calcium oxide, tantalum oxide, silicon oxide, and barium oxide and the recovered phosphor is formed inside the partition walls. ), A phosphor is fixed thereon, and a phosphor pattern is formed.

Thus, according to the method of the present invention,
A phosphor pattern can be formed uniformly without causing pattern defects during firing, and alumina, titanium oxide, yttrium oxide, magnesium oxide, calcium oxide, tantalum oxide can be formed between the phosphor layer and the partition wall surface. Since the reflection layer (A) containing the inorganic compound (a) selected from white pigments such as silicon oxide and barium oxide and the recovered phosphor is provided, the luminance of the phosphor is improved. Further, in the method of the present invention, by providing the reflective layer (A), the thickness of the phosphor-containing layer (B) can be reduced as compared with the case where the reflective layer (A) is not provided. The amount of body used can be reduced, and furthermore, by using the recovered phosphor in the reflective layer (A), the used phosphor can be effectively reused, which is economical and It is also an environmentally friendly method.

Also, full-color P
In order to form DP, inorganic pigments selected from white pigments such as alumina, titanium oxide, yttrium oxide, magnesium oxide, calcium oxide, tantalum oxide, silicon oxide, barium oxide, or red, green, and blue recovered phosphors Using the reflection layer (A) containing the compound (a) and the respective red, green, and blue phosphor-containing layers (B), the above-mentioned (the formation of the reflection layer (A) and the phosphor-containing layer (B ) Is repeated, and the phosphors of the above three colors (R (red), G (green), and B (blue)) are filled in the partition walls, and then (firing) is performed. It can be made.

[0040]

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 [Production of dry film (F1) comprising reflective layer (A)] The following inorganic compound (a), base polymer (b),
Reflective layer (A) by mixing ethylenically unsaturated compound (c)
The resin composition used for was prepared.

57 parts of inorganic compound (a) / alumina (manufactured by Kishida Co.) Base polymer (b) The copolymerization ratio of methyl methacrylate / methacrylate / 2-ethylhexyl acrylate / styrene / acrylic acid / methacrylic acid is on a weight basis. 25 parts of a copolymer having a ratio of 58/5/11/3/1/22 (acid value: 151.0 mgK OH / g, glass transition temperature: 79.0 ° C., weight average molecular weight: 80,000)

Ethylene unsaturated compound (c) / glycerin triacrylate (manufactured by Daicel UBC, "OTA-480") 18 parts ・ Ethylene oxide-modified phthalic acid acrylate 10 parts ・ Trimethylolpropane triacrylate 10 parts

Next, the obtained resin composition was filled in gap 3
Using a mill applicator, coat on a 20 μm-thick polyester film, leave at room temperature for 1 minute and 30 seconds, and in an oven at 60 ° C., 90 ° C., and 110 ° C. for 3 minutes each.
Drying was performed for every minute to produce a dry film (F1) having _a thickness (ha) of 20 μm (however, no protective film was provided).

[Production of dry film (F2) comprising phosphor-containing layer (B)] The following base polymer (d), ethylenically unsaturated compound (e), photopolymerization initiator (f) and phosphor (g) ) Was mixed to prepare a resin composition used for the phosphor-containing layer (B).

Base polymer (d) : A copolymer having a copolymerization ratio of methyl methacrylate / methacrylate / 2-ethylhexyl acrylate / styrene / acrylic acid / methacrylic acid of 58/5/11/3/3/22 by weight. 25 parts of polymer (acid value: 151.0 mgK OH / g, glass transition temperature: 79.0 ° C, weight average molecular weight: 80,000)

Ethylene unsaturated compound (e) glycerin triacrylate (manufactured by Daicel UBC, "OTA-480") 18 parts Ethylene oxide-modified phthalic acid acrylate 10 parts Trimethylolpropane triacrylate 10 parts

Photopolymerization initiator (f) 7 parts of benzophenone 0.1 part of 4,4'-diethylaminobenzophenone 0.1 part of ethyl P-dimethylbenzoate

Phosphor (g) .Y ₂ O ₂ S: Eu (emission wavelength: 642 nm, particle size: 2.2 ± 0.5 μm, specific gravity: 5.1) 57 parts

Next, the obtained resin composition was filled in gap 3
Using a mill applicator, coat on a 20 μm-thick polyester film, leave at room temperature for 1 minute and 30 seconds, and in an oven at 60 ° C., 90 ° C., and 110 ° C. for 3 minutes each.
Each minute was dried to produce a dry film (F2) having a thickness (h _b ) of 20 μm (however, no protective film was provided). Using the obtained dry film (F1) composed of the reflective layer (A) and the dry film (F2) composed of the phosphor-containing layer (B), a phosphor pattern was formed in the following manner.

(Formation of Reflective Layer (A) and Phosphor-Containing Layer (B)) Partition walls (height (h ₀ )) preheated to 60 ° C. in an oven
A PDP substrate (200 mm × 100 mm × 100 μm, width 80 μm, slit 150 μm)
200 mm × 2 mm), a dry film (F1) comprising the above-mentioned reflective layer (A) was laminated at a temperature of 100 ° C., a roll pressure of 3 kg / cm ² , and a lamination speed of 1.0 m / min.
After laminating under the conditions, the polyester film was peeled off, and a dry film (F2) composed of the phosphor-containing layer (B) was similarly laminated on the polyester film to form a reflective layer (A)
And phosphor-containing layer (B) was formed _{(h a / h b = 50} /
50).

(Exposure and Development) Next, a pattern mask is placed on the entire surface of the polyester film on the surface of the phosphor-containing layer (B) such that the inside of the partition (except for the upper part of the partition) is exposed, and an Exposure machine “HMW-
532D "at 80 mj with a 3 kW ultra-high pressure mercury lamp. After taking a hold time of 15 minutes after exposure,
% Sodium carbonate aqueous solution at 30 ° C. for 1.5 times 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, and
The temperature is raised to 0 ° C. to burn off the resin components in the reflection layer (A) and the phosphor-containing layer (B), fix the inorganic compound and the phosphor in the partition walls, and form a red, green, and blue phosphor pattern. Was formed. In the above process, the following evaluation was performed.

(Evaluation of Luminance of Phosphor) After forming the red line as described above, baking to form a red phosphor pattern, irradiating ultraviolet light of 254 nm to cause the phosphor to emit light, the luminance meter ( PHOTORESEARCH, "P
The luminance (T ₁ ) was measured using an R-650 spectrophotometer ”). The evaluation was performed using the luminance (T) measured in Comparative Example 1 described later.
₀ ) as a reference (1.00), and the ratio (T ₁ / T
₀ ).

Example 2 In Example 1, the inorganic compound (a) in the reflection layer (A) was used.
Was performed in the same manner except that the following was changed, and the inorganic compound and the phosphor were fixed in the partition walls to form red, green, and blue phosphor patterns.

Recovered phosphor of inorganic compound (a) .Y ₂ O ₂ S: Eu (phosphor once used for forming a phosphor pattern, developed and recovered) In the above process, the same evaluation as in Example 1 was performed. Was done.
Further, since the above-mentioned recovered phosphor is used as the inorganic compound (a), it is economical and does not generate waste material and is environmentally excellent.

Comparative Example 1 The procedure of Example 1 was repeated except that the reflective layer (A) was not provided, and only the phosphor-containing layer (B) (20 μm) was provided in the partition. Then, red, green and blue phosphor patterns were formed. In the above process, Example 1
The evaluation was performed in the same manner as described above.

Comparative Example 2 The procedure of Example 1 was repeated except that the reflective layer (A) was changed to a white dielectric layer. The inorganic compound and the phosphor were fixed in the partition walls, and the red, green and blue phosphors were used. A pattern was formed.
In the above process, the same evaluation as in Example 1 was performed. Table 1 shows the results of Examples and Comparative Examples.

[0059]

[0060]

The method for forming a phosphor pattern according to the present invention comprises:
Alumina, titanium oxide, yttrium oxide, magnesium oxide, calcium oxide, tantalum oxide, silicon oxide,
Since the reflective layer (A) containing an inorganic compound (a) selected from a white pigment such as barium oxide or a recovered phosphor and the phosphor-containing layer (B) are formed so as to be filled in the partition walls. In addition, the phosphor can be efficiently and uniformly formed on the side walls and the bottom of the partition wall, and the luminance of the phosphor can be improved.
It is very useful for forming phosphors such as DP. When the recovered phosphor is used as the inorganic compound (a), the phosphor used as a waste material is reused, which leads to a significant cost reduction and is economical, and is a method that is environmentally friendly.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Keinosuke Hirai 2-13-1, Muroyama, Ibaraki-shi, Osaka Japan Central Research Laboratory, Japan Chemical Industry Co., Ltd. (72) Inventor Shigeo Kasahara Kamihara-ku, Kawasaki-shi, Kanagawa 4-1-1 Odanaka Fujitsu Limited (72) Inventor Nobuhiro Iwase 4-1-1 Kamiodanaka Nakahara-ku, Kawasaki City, Kanagawa Prefecture Fujitsu Limited (72) Inventor Hitoshi Yamada Nakahara-ku, Kawasaki City, Kanagawa Prefecture 4-1-1 Odanaka Fujitsu Limited F-term (reference) 5C028 FF14 5C040 GA03 GG01 GG09 JA15 JA21 MA26 MA30

Claims (8)

[Claims] When a phosphor pattern is formed in a partition of a plasma display panel, alumina, titanium oxide, yttrium oxide, magnesium oxide, calcium oxide, tantalum oxide, silicon oxide, barium oxide, and recovered fluorescent light are formed in the partition. After forming a reflective layer (A) containing an inorganic compound (a) selected from a body and a layer provided with a phosphor-containing layer (B) thereon, exposure, development, and baking are performed. A method for forming a characteristic phosphor pattern. 2. The inorganic compound (a) wherein the reflection layer (A) is selected from alumina, titanium oxide, yttrium oxide, magnesium oxide, calcium oxide, tantalum oxide, silicon oxide, barium oxide, and a recovered phosphor, and a base polymer. 2. The method according to claim 1, wherein (b) comprises an ethylenically unsaturated compound (c). 3. The phosphor-containing layer (B) comprises a base polymer (d), an ethylenically unsaturated compound (e), a photopolymerization initiator (f) and a phosphor (g). Item 3. The method for forming a phosphor pattern according to Item 1 or 2. 4. The plasma display panel according to claim 1, wherein a reflecting layer (A) is provided in a partition wall of the plasma display panel, and then a phosphor-containing layer (B) is provided thereon. A method for forming a phosphor pattern. 5. A dry film (F) in which a reflective layer (A) is laminated on a support film in providing a reflective layer (A).
5. The method of forming a phosphor pattern according to claim 1, wherein 1) is used. 6. In providing the phosphor-containing layer (B),
A dry film (F2) in which a phosphor-containing layer (B) is laminated on a support film is used.
5. The method for forming a phosphor pattern according to any one of 5. 7. When forming a phosphor pattern in a partition wall of a plasma display panel, a laminate of a reflection layer (A) and a phosphor-containing layer (B) formed in a sheet or film shape in advance is reflected. In a state where the layer (A) is on the side of the partition wall, the phosphor layer (B) is formed on both the side surface and the bottom surface of the partition wall by being pushed into the partition wall, further patterned into a partition shape and baked. 7. The method for forming a phosphor pattern according to claim 1, 2, 3, 5, or 6. 8. The method according to claim 1, wherein
A phosphor pattern of three colors of R (red), G (green) and B (blue).