JP2001057151A - Forming method for phosphor pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To optimize for a post-process for providing an ITO electrode and a scattering layer, by filling a photosensitive resin composite comprising an ethylene unsaturated compound and a self-cleaving type photopolymerization starting agent in the recessed part of a resist pattern containing a phosphor and causing photocuring after forming the resist pattern containing the phosphor. SOLUTION: In this forming method for a phosphor pattern, after a resist pattern 2 containing a phosphor is formed by laminating a photosensitive resin composite containing a phosphor is laminated on a substrate and carrying out exposure and development, a photosensitive resin composite (D) 3 comprising an ethylene unsaturated compound and a self cleaving type photopolymerization starting agent is filled in the recessed part of the resist pattern 2 containing a phosphor, and photocuring is caused. A smooth phosphor pattern against the surface of the substrate can be obtained by this method, and excellent luminous intensity is given by irradiating ultraviolet rays with a long wavelength. It is especially significant when a photopolymerization starting agent so as to make ultraviolet-ray transmittance 80% of higher at 365 nm of the photosensitive resin composite after exposure is used as the self-cleaving photopolymerization starting agent.

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, and more particularly, to a method for forming a phosphor pattern capable of obtaining a phosphor display having excellent emission intensity under irradiation with ultraviolet light having a long wavelength. .

[0002]

2. Description of the Related Art In recent years, PDPs utilizing phosphor patterns have been developed.
(Plasma Display Panels) and other flat display panels are being actively developed. From the display screen of a laptop personal computer to various electronic bulletin boards,
The use thereof has been expanding to a so-called "wall-mounted television", and a phosphor-containing photosensitive resin composition has been used in forming such a phosphor pattern.

In general, when forming a phosphor pattern on a substrate such as glass, a phosphor-containing photosensitive resin composition as described in JP-A-6-273925 is used.
Irradiation with ultraviolet light, exposure and development are performed, and then baking is performed to form a phosphor pattern. At this time, as the ultraviolet rays at the time of exposure, ultraviolet rays having a long wavelength are usually used. Next, the phosphor on which the pattern is formed is irradiated with ultraviolet rays to emit light from the phosphor.

[0004]

However, the technique disclosed in Japanese Patent Application Laid-Open No. Hei 6-273925 is to form a pattern of only a phosphor on a substrate by performing baking after development. When an ITO electrode or a scattering layer is provided on the phosphor pattern, the phosphor-containing photosensitive resin composition having a thickness of 1 to 500 μm is used instead of the powder alone due to the low cohesion of the powder. It was necessary to obtain a cured resist layer. Furthermore, in consideration of the influence of the unevenness of the phosphor pattern, it is necessary to smooth the substrate surface.

In addition, when the phosphor emits light, the phosphor-containing photosensitive resin composition using a usual photopolymerization initiator absorbs the irradiated long-wavelength ultraviolet rays and inhibits the emission of the phosphor. Therefore, there is a problem that the emission intensity is reduced. In order to prevent such a problem, it is necessary to irradiate the phosphor by irradiating short-wavelength ultraviolet rays that are not absorbed by the photopolymerization initiator. The fluorescent display must correspond to the ultraviolet light of the wavelength.

Therefore, in the present invention, under such a background, the phosphor pattern formed on the substrate is smooth with respect to the substrate surface, and is most suitable for a post-process such as providing an ITO electrode or a scattering layer, and It is an object of the present invention to provide a method for forming a phosphor pattern which is excellent in the emission intensity of the phosphor even when irradiating long-wavelength ultraviolet rays.

[0007]

Means for Solving the Problems However, as a result of intensive studies in view of the above circumstances, the present inventor has laminated a phosphor-containing photosensitive resin composition (A) on a substrate, and exposed and developed the resin. After forming the phosphor-containing resist pattern, a photosensitive resin composition (D) comprising an ethylenically unsaturated compound (B) and a self-cleavable photopolymerization initiator (C) is filled in the concave portions of the phosphor-containing resist pattern. Filling, the method of forming a photocurable phosphor pattern, a smooth phosphor pattern is obtained on the substrate surface, it has been found that in the long-wavelength ultraviolet irradiation, has an excellent emission intensity, the present invention has been completed. .

In the present invention, as the self-cleaving photopolymerization initiator (C), 365 n of the photosensitive resin composition after exposure is used.
When a photopolymerization initiator having an ultraviolet transmittance of 80% or more at m is used, a particularly remarkable effect is exhibited. Further, in the present invention, the phosphor-containing photosensitive resin composition (A) comprises a carboxyl group-containing acrylic polymer (E), an ethylenically unsaturated compound (F), a self-cleavable photopolymerization initiator (G), and a phosphor. (H) shows a particularly remarkable effect.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
FIG. 1 shows a phosphor pattern obtained by the method for forming a phosphor pattern of the present invention. The phosphor-containing photosensitive resin composition (A) of the present invention comprises a carboxyl group-containing acrylic polymer (E), an ethylenically unsaturated compound (F), a self-cleavable photopolymerization initiator (G), and a phosphor (H). ) Is preferable. As the carboxyl group-containing acrylic polymer (E), an acrylic copolymer containing (meth) acrylate as a main component and copolymerizing an ethylenically unsaturated carboxylic acid or another copolymerizable monomer is used. An acetoacetyl group-containing acrylic copolymer can also be used. Further, if necessary, a polyester-based resin or a polyurethane-based resin may be used in combination.

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.

The ethylenically unsaturated carboxylic acid is 15 to 30.
About 100% by weight (about 100-200mgKOH / g in acid value)
It is preferred to copolymerize. Examples of other copolymerizable monomers include acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, and alkyl vinyl ether.

As the ethylenically unsaturated compound (F),
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, diglycidyl phthalate di (meth) acrylate, glycerin triacrylate, glycerin poly Examples include polyfunctional monomers such as glycidyl 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-hydroxypropyl phthalate, 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 can be mentioned.

The compounding ratio of the ethylenically unsaturated compound (F) is based on the carboxyl group-containing acrylic polymer (E) 10
The amount is preferably from 10 to 200 parts by weight, particularly preferably from 40 to 100 parts by weight, based on 0 parts by weight. Too little ethylenically unsaturated compound (F) results in poor curing, reduced flexibility, and delayed development speed, while too much ethylenically unsaturated compound (F) increases tackiness, cold flow, and peeling of the cured resist. This results in a reduction in speed.

The photopolymerization initiator (G) used in the present invention is not particularly limited as long as it is a self-cleaving type. Preferably, the carboxyl group-containing acrylic polymer (E) and the ethylenically unsaturated compound are used. When the photosensitive resin composition comprising (F) and the self-cleavable photopolymerization initiator (G) is exposed to light, it has an ultraviolet transmittance at 365 nm of 80.
%, Preferably 80 to 95%. The ultraviolet transmittance is 80%
If it is less than 1, the luminance of the phosphor in the phosphor-containing photosensitive resin composition is extremely lowered, which is not preferable.

The self-cleaving photopolymerization initiator (G) includes, for example, benzoin, benzoin methyl ether,
Benzoyl isopropyl ether, benzoin isobutyl ether, benzoin butyl ether, 2,2-dihydroxy-2-phenylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1-hydroxy-
Examples thereof include cyclohexyl-phenyl-ketone, and among them, 2,2-dimethoxy-2-phenylacetophenone is particularly preferably used.

Here, the ultraviolet transmittance at 365 nm of the photosensitive resin composition containing the carboxyl group-containing acrylic polymer (E), the ethylenically unsaturated compound (F) and the self-cleavable photopolymerization initiator (G) is determined. Paste on glass, 36
After exposure with ultraviolet light of 5 nm, an ultraviolet transmittance measurement device (P
HOTO RESEARCH, "PR-650 spectrophotometer").

In the present invention, only the above-mentioned self-cleavable photopolymerization initiator (G) is used as the photopolymerization initiator, and the content of the self-cleavable photopolymerization initiator (G) is a carboxyl group-containing photopolymerization initiator. 0.1 parts by weight based on 100 parts by weight of the total of the acrylic polymer (E) and the ethylenically unsaturated compound (F)
The amount is preferably from 10 to 10 parts by weight, particularly preferably from 0.5 to 3 parts by weight. If the content of the self-cleaving photopolymerization initiator (G) is less than 0.1 part by weight, the film strength will be reduced due to poor curing, and if it exceeds 10 parts by weight, it will be undesirably left as an impurity during preparation.

The phosphor (H) used in the present invention is not particularly limited as long as it excites and emits light with ultraviolet light having a long wavelength. For example, ZnS; Ag, Al, Zn
S; Cu, Al, ZnS; Ag, (Zn, Cd) S; C
u, Al, Y ₂ O ₂ S; Eu, ZnO; Zn and the like, and these are used alone or in combination of two or more.

The content of the phosphor (H) is preferably 30 to 180 parts by weight, more preferably 100 parts by weight of the total of the carboxyl group-containing acrylic polymer (E) and the ethylenically unsaturated compound (F). Is 50 to 160 parts by weight. If the content is less than 30 parts by weight, the emission luminance will be insufficient, and if it exceeds 180 parts by weight, it will be difficult to form a film described later, which is not preferable. The method for incorporating the phosphor (H) is not particularly limited, and a known method, for example, a predetermined amount of the phosphor (H) is added to the above-mentioned photosensitive resin composition, and the mixture is sufficiently mixed and stirred to form the phosphor. There is a method of uniformly dispersing.

Further, the above-mentioned phosphor-containing photosensitive resin composition (A) may further comprise a dye (colored or colored), an adhesion-imparting agent, a plasticizer, an antioxidant, a thermal polymerization inhibitor, a solvent, and a surface tension. Additives such as modifiers, stabilizers, chain transfer agents, defoamers, and flame retardants can also be added as appropriate. It is preferable that the phosphor-containing photosensitive resin composition (A) is formed into a film in advance. Specifically, the photosensitive resin composition comprising the above (E) to (H) is laminated on a dry film resist. It is preferable to provide the phosphor (photoresist film) for forming a phosphor pattern thereafter.

In the present invention, the above-mentioned phosphor-containing photosensitive resin composition (A) is laminated on a substrate, exposed and developed to form a phosphor-containing resist pattern. A photosensitive resin composition (D) comprising an ethylenically unsaturated compound (B) and a self-cleavable photopolymerization initiator (C), and photo-cured to form a phosphor pattern. A method for forming such a phosphor pattern will be specifically described.

(Lamination Method) The above-mentioned phosphor-containing photosensitive resin composition (A) is applied to a base film surface such as a polyester film, a polypropylene film, a polystyrene film, etc., and then a polyethylene film or a polyvinyl alcohol is coated on the coated surface. A protective film such as a base film is coated to form a laminate for a dry film. At this time, the film thickness of the phosphor-containing photosensitive resin composition varies depending on the phosphor content or the like, and cannot be unconditionally determined, but is usually 10 to 200 μm.
m is preferred.

(Exposure) In order to form an image using the dry film resist, the adhesive strength between the base film and the phosphor-containing photosensitive resin composition layer and the adhesion between the protective film and the phosphor-containing photosensitive resin composition layer Compare the strength, peel off the film with the lower adhesive strength, laminate the phosphor-containing photosensitive resin composition layer side on a substrate such as glass, metal, or plastic, and then pattern mask on the other film. Is exposed to light. At this time, if necessary, two or more dry film resists can be laminated. The conditions for lamination are not particularly limited. For example, the laminating roll temperature is 40 to 150 ° C. and the roll pressure is 1 to 5
kg / cm ² , and the laminating speed is 0.1 to 5 m / min.

When the photosensitive resin composition has no tackiness, the other film may be peeled off, and then the pattern mask may be brought into direct contact with the photosensitive resin composition layer for exposure. Exposure is usually performed at a long wavelength (300 to 400 n
m) by irradiation with ultraviolet light.
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 and the like are used. After UV irradiation, heat if necessary,
Complete curing can be achieved.

(Development) After exposure, the film on the resist is peeled off and developed. Since the above-mentioned phosphor-containing photosensitive resin composition (A) is a dilute alkali developing type, development after exposure is performed using a dilute aqueous solution of about 0.5 to 2% by weight of an alkali such as sodium carbonate and potassium carbonate. Do. At this time, it is also possible to use a developer such as an organic alkali. By such development, a phosphor-containing resist pattern is formed.

(Filling of Photosensitive Resin Composition (D)) After development, the ethylenically unsaturated compound (B) and the self-cleavable photopolymerization initiator (C) are added to the recesses of the obtained phosphor-containing resist pattern. The photosensitive resin composition (D). When filling the photosensitive resin composition (D), the filling may be performed up to the height of the concave portion of the phosphor-containing resist pattern to smooth the upper portion, or the filling may be performed by filling 1 to 50 μm higher than the height of the concave portion to make the upper surface smooth. 1). The filling method is not particularly limited. For example, a method in which the photosensitive resin composition (D) is poured directly into the concave portions of the obtained phosphor-containing resist pattern and the upper portion is rubbed with a squeegee or the like, or a mirror support (glass) , SUS, etc.), a method of dropping the photosensitive resin composition (D), covering the phosphor-containing resist pattern downward from above, and removing and filling the air bubbles. Among them, a method in terms of surface smoothness is preferred.

The ethylenically unsaturated compound (B) is not particularly restricted but includes, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, β-acryloyloxypropyl hydrogen phthalate, glycerin tri ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylol methane tri (meth) acrylate, bisphenol A di (meth) acrylate or an ethylene oxide modified product thereof, among which bisphenol A type di (meth) acrylate Modified ethylene oxide is preferably used.

The self-cleaving type photopolymerization initiator (C) is not particularly limited as long as it is a self-cleaving type, but it is preferably 365 nm of the photopolymerized photosensitive resin composition (D).
Has an ultraviolet transmittance of 80% or more, preferably 80 to
It is desired to use a photopolymerization initiator having a content of 95%. If the UV transmittance is less than 80%, the luminance at the time of emitting the phosphor is extremely reduced, which is not preferable. here,
The ultraviolet transmittance at 365 nm was determined by measuring the ultraviolet transmittance after applying a photosensitive resin composition containing an ethylenically unsaturated compound (B) and a self-cleaving photopolymerization initiator (C) to glass and exposing the composition to ultraviolet light at 365 nm. Tableware (PHOTO RE
It is measured by SEARCH Co., Ltd., "PR-650 spectrophotometer".

Examples of the self-cleaving photopolymerization initiator (C) include, for example, benzoin, benzoin methyl ether, benzoyl isopropyl ether, benzoin isobutyl ether, benzoin butyl ether similar to the above-mentioned self-cleaving photopolymerization initiator (G). 2,2-dihydroxy-2-phenylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-
2-phenylacetophenone, 1-hydroxy-cyclohexyl-phenyl-ketone and the like.
2-Dimethoxy-2-phenylacetophenone is particularly preferably used.

The photosensitive resin composition (D) comprises the above ethylenically unsaturated compound (B) and a self-cleavable photopolymerization initiator (C). Regarding the mixing ratio of the photopolymerization initiator (C),
The content of the self-cleaving photopolymerization initiator (C) is preferably 0.5 to 10% by weight, more preferably, the total amount of the ethylenically unsaturated compound (B) and the self-cleaving photopolymerization initiator (C). It is 1 to 5% by weight, particularly preferably 1 to 2% by weight. If the compounding ratio is less than 0.5% by weight, poor curing occurs, and if it exceeds 10% by weight, the photopolymerization initiator becomes insoluble, which is not preferable.

(Photocuring) After the photosensitive resin composition (D) has been filled into the recesses of the phosphor-containing resist pattern obtained by the previous development, the photosensitive resin composition (D) is photocured by irradiation with ultraviolet rays. I do. For photo-curing, the wavelength is 300 ~
The irradiation is preferably performed using ultraviolet light having a wavelength of 400 nm. As the light source, 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 curing, a smooth phosphor pattern is formed on the substrate surface (see FIG. 1).

Thus, according to the method of the present invention, a smooth phosphor pattern can be formed on the entire surface of a substrate such as glass, metal or plastic. or,
In the present invention, since a specific photopolymerization initiator is used, after development, without firing, 300 to 4
The phosphor can emit light by irradiating ultraviolet light having a long wavelength of 00 nm. In the irradiation of the ultraviolet light,
It can be performed using the exposure machine used at the time of the above exposure,
Even with long-wavelength ultraviolet irradiation, it has an excellent effect on light emission intensity.

[0035]

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 The following carboxyl group-containing acrylic polymer (E) 2
0.5 part, the following ethylenically unsaturated compound (F) 19 parts, the following photopolymerization initiator (G) 0.5 part and the following phosphor (H) 60 parts were mixed, and the phosphor-containing photosensitive material was mixed. The dope of the resin composition (A) was adjusted (solvent: methyl ethyl ketone).

Carboxyl group-containing acrylic polymer
(E) The copolymerization ratio of methyl methacrylate / methacrylate / 2-ethylhexyl acrylate / styrene / acrylic acid / methacrylic acid is 58/5/11/3/1 on a weight basis.
/ 22 (acid value 151.0 mg KOH /
g, glass transition point 79.0 ° C, weight average molecular weight 80,000)

15 parts of ethylenically unsaturated compound (F) / glycerin triacrylate ("OTA-480" manufactured by Daicel UBC) 4 parts of polyethylene glycol dimethacrylate

[0039] photopolymerization initiator (G) · 2,2-dimethoxy-2-phenyl acetophenone (Ciba-Geigy Corp., "Irgacure 651") phosphor _{(H) · Y 2 O 2} S: Eu ( emission wavelength; 626 nm , Particle size: 5.1 μm)

Next, the obtained dope was coated on a polyester film having a thickness of 20 μm by using an applicator having a gap of 5 mil, left at room temperature for 1 minute 30 seconds, and then dried.
The resultant was dried in an oven at 0 ° C., 90 ° C., and 110 ° C. for 3 minutes each to prepare a dry film resist including a phosphor-containing photosensitive resin composition layer having a resist thickness of 20 μm. (However, no protective film is provided).

The photosensitive resin composition layer side of the dry film resist was brought into contact with a glass substrate (200 mm × 200 mm × 2 mm) preheated to 60 ° C. in an oven.
Laminate roll temperature 100 ° C, roll pressure 3kg / cm
^2. Lamination was performed at a lamination speed of 1.0 m / min.

(Exposure and development) After lamination, a transparent silver halide film mask is placed on the entire surface of the polyester film so as to be exposed at a pitch of 100 μm, up, down, left and right, and 200 μm. 53
Exposure was performed at 80 mj using a 3 kW ultrahigh pressure mercury lamp in 2D. (The wavelength of the ultraviolet light used for exposure was 365 nm.) In addition, at 365 nm after exposure of the photosensitive resin composition comprising a carboxyl group-containing acrylic polymer, an ethylenically unsaturated compound, and a self-cleavable photopolymerization initiator. The ultraviolet transmittance was 80%. After a 15-minute hold time after exposure, development was performed at 30 ° C. in a 1% aqueous sodium carbonate solution for 1.5 times the minimum development time.

(Filling and Photocuring of Photosensitive Resin Composition (D)) The following photosensitive resin composition (D) is dropped on a smooth glass surface, and a phosphor-containing resist obtained by the above development is dropped thereon. The pattern was covered with the dot side down, air bubbles were completely removed by evacuation, and the glass was exposed to 1000 mj from the glass side using long-wavelength ultraviolet light and photocured.
After the exposure, the glass is peeled off to form the phosphor pattern of the present invention (the phosphor-containing resist pattern has a thickness of 20 μm,
A thickness of the photosensitive resin composition (D) from the substrate of 25 μm),
A fluorescent display was obtained. The obtained phosphor pattern was smooth with respect to the substrate surface.

As the ethylenically unsaturated compound (B) of the photosensitive resin composition (D ), 99 parts of bisphenol A type ethylene oxide 4 mol-modified dimethacrylate (“BP-4EA” manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and As the self-cleaving photopolymerization initiator (C), 2,2-
One part of dimethoxy-2-phenylacetophenone (manufactured by Ciba Geigy, "Irgacure 651") was mixed and prepared. Incidentally, 365 of the photosensitive resin composition (D) after the exposure was used.
The ultraviolet transmittance in nm was 80%.

For the obtained fluorescent display, 365 nm
Irradiation from the overcoat layer side using a long-wavelength ultraviolet lamp of PHOTO RESEARCH
The light emission intensity was measured by "PR-650 spectral colorimeter" manufactured by Company H.

Example 2 A phosphor was prepared in the same manner as in Example 1 except that the photopolymerization initiator (G) was changed to 1-hydroxy-cyclohexyl-phenyl-ketone ("Irgacure 184", manufactured by Ciba Geigy). A photosensitive resin composition was prepared, and a phosphor pattern was formed in the same manner as in Example 1 (the thickness of the phosphor-containing resist pattern was 20 μm) to obtain a fluorescent display. The obtained phosphor pattern was smooth with respect to the substrate surface. In addition, a carboxyl group-containing acrylic polymer,
When the photosensitive resin composition comprising the ethylenically unsaturated compound and the photopolymerization initiator was exposed, the ultraviolet ray transmittance at 365 nm was 60%. The emission intensity of the obtained fluorescent display was measured in the same manner as in Example 1.

Example 3 In Example 1, the following photosensitive resin composition resin (D)
The phosphor pattern was formed in the same manner as in Example 1 except that the phosphor display was obtained. The obtained phosphor pattern was smooth with respect to the substrate surface.

As the photosensitive resin composition (D) , the ethylenically unsaturated compound (B) may be glycerin triacrylate ("OTA-" manufactured by Daicel UCB Co., Ltd.).
480 ") 99 parts and a self-cleaving photopolymerization initiator (C)
1-hydroxy-cyclohexyl-phenyl-
Ketone (Ciba Geigy, “IRGACURE 18
4 ") 1 part was mixed and prepared. In addition, the ultraviolet transmittance at 365 nm of the photosensitive resin composition (D) after exposure is 6
It was 0%. The emission intensity of the obtained fluorescent display was measured in the same manner as in Example 1.

Comparative Example 1 The procedure of Example 1 was repeated, except that the following photosensitive resin composition was used. A phosphor pattern was formed in the same manner as in Example 1 to obtain a fluorescent display.

As the ethylenically unsaturated compound (B) of the photosensitive resin composition, 99 parts of bisphenol A type ethylene oxide 4 mol modified dimethacrylate (“BP-4EA”, manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and a photopolymerization initiator As benzophenone / 4,4 '
-Diethylaminobenzophenone / 2,2-bis (o-
Chlorophenyl) 4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole (mixing weight ratio 8 / 0.15
/ 1) 1 part was mixed and prepared. The ultraviolet transmittance at 365 nm of the photosensitive resin composition after exposure was 30%. The emission intensity of the obtained fluorescent display was measured in the same manner as in Example 1. Table 1 shows the results of Examples and Comparative Examples.
For evaluation, the luminance obtained in Example 1 was set to 100
And the ratio when it is shown.

[0051]

[Table 1]

[0052]

The method for forming a phosphor pattern according to the present invention comprises:
A phosphor-containing photosensitive resin composition (A) is laminated on a substrate,
After performing exposure and development to form a phosphor-containing resist pattern, a photosensitive resin comprising an ethylenically unsaturated compound (B) and a self-cleavable photopolymerization initiator (C) is formed in a concave portion of the phosphor-containing resist pattern. Since the composition (D) is filled and light-cured, the phosphor pattern formed on the substrate is smooth with respect to the substrate surface, and is suitable for a post-process such as providing an ITO electrode or a scattering layer, and has a long length. It also shows an excellent effect on the emission intensity of the phosphor even when irradiating ultraviolet light with a wavelength.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram of a phosphor pattern formed by a method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Substrate 2 ... Phosphor containing resist pattern 3 ... Photosensitive resin composition (D)

Claims (4)

[Claims] 1. A phosphor-containing photosensitive resin composition (A) is laminated on a substrate, exposed and developed to form a phosphor-containing resist pattern. Resin composition (D) comprising a water-soluble unsaturated compound (B) and a self-cleavable photopolymerization initiator (C)
And forming a phosphor pattern by photo-curing. 2. Self-cleaving photopolymerization initiator (C)
2. The method for emitting a phosphor according to claim 1, wherein a photopolymerization initiator is used such that the UV transmittance at 365 nm of the photosensitive resin composition after exposure is 80% or more. 3. The phosphor-containing photosensitive resin composition (A) comprises:
2. The phosphor pattern according to claim 1, comprising a carboxyl group-containing acrylic polymer (E), an ethylenically unsaturated compound (F), a self-cleavable photopolymerization initiator (G), and a phosphor (H). Formation method. 4. As the phosphor (H), ZnS; Ag, A
l, ZnS; Cu, Al, ZnS; Ag, (Zn, C
4. The method for forming a phosphor pattern according to claim 1, wherein one or more of d) S, Cu, Al, Y ₂ O ₂ S, Eu, ZnO and Zn are used.