JPH10142786A - Photoresist film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photoreslst layer having excellent follow-up property to a base (such as a cell) and excellent dispersion stability of a phosphor by incorporating a base polymer, ethylenetype unsatd. compd. and phosphor and controlling the ratio of the base polymer to the ethylene type unsatd. compd. to a specified range. SOLUTION: A photosensitive resin compsn. containing a base polymer. ethylene-type unsatd. compd. and phosphor and has the weight ratio of the base polymer to the ethylene type unsatd. compd. between 100/120 to 100/150 is laminated on a base film. As for the base polymer, an acryl resin, polyester resin, polyurethane resin, etc., can be used. As for the ethylene-type unsatd. compd., polyfunctional monomers such as ethylene glycol di(meth)acrylate and diethylene glycol di(meth)acrylate can be used, and these monomers are preferably used with bifunctional and trifunctional monomers. The phosphor is preferably a rare earth oxihallde as the main component and activated with an activating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoresist film using a photosensitive resin composition containing a phosphor, and more particularly, to a photoresist film useful for producing a fluorescent display such as a plasma display.

[0002]

2. Description of the Related Art Recently, various flat panel displays have been actively developed. Among them, a plasma display panel (PDP) has attracted attention. Its use is expanding to the so-called “wall-mounted TV”.
Then, a phosphor for display is applied to the cells of the display panel of the PDP, and the phosphor is colored by ultraviolet rays generated in the gas sealed in the cell by an applied voltage. Conventionally, a liquid photoresist in which phosphors of each color are dispersed has been used as such a phosphor, but the present applicant has replaced such a liquid photoresist with a dry film resist containing a phosphor (photoresist film). ) Proposed. (JP-A-6-273925)

[0003]

However, as a result of further study on the above-mentioned photoresist film, it has been found that there is still room for improvement in followability of the photoresist film to cells.

[0004]

The inventors of the present invention have conducted intensive studies on the conformability of a photoresist film to cells, and as a result, have found that a base film containing an ethylenically unsaturated compound, a phosphor and a base polymer. And the content ratio of the ethylenically unsaturated compound is 100/120 to 100/1
It has been found that a photoresist film obtained by laminating a photosensitive resin composition having a weight ratio of 50 to a base film has excellent followability to cells and excellent dispersibility of a phosphor. When glycerin acrylate is used as the unsaturated compound, the effects of the present invention have been found to be more remarkable, and the present invention has been completed.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The photosensitive resin composition of the present invention comprises a base polymer (A), an ethylenically unsaturated compound (B), a photopolymerization initiator (C) and a phosphor (D). For example, an acrylic resin, a polyester resin, a polyurethane resin, or the like is used. Among these, acrylic copolymers containing (meth) acrylate as a main component and optionally copolymerizing an ethylenically unsaturated carboxylic acid or another copolymerizable monomer are important. An acetoacetyl group-containing acrylic copolymer can also be used. Here, as the (meth) acrylic acid ester,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth)
Acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, Glycidyl (meth) acrylate is exemplified.

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.

In the case of the development with a rare alkali, the ethylenically unsaturated carboxylic acid is added in an amount of about 15 to 30% by weight (acid value of 1 to 30% by weight).
(About 200 to 200 mg KOH / g). Examples of other copolymerizable monomers include acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, and alkyl vinyl ether.

As the ethylenically unsaturated compound (B),
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 thereof include polyfunctional monomers such as glycidyl ether poly (meth) acrylate. A combination of a bifunctional monomer and a trifunctional monomer is preferable, and a glycerin-modified triacrylate is particularly preferable as the trifunctional monomer.

An appropriate amount of a monofunctional monomer can be used in combination with these polyfunctional monomers. Examples of the 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.

In the present invention, the base polymer (A)
And the control of the content ratio of the ethylenically unsaturated compound (B) to a specific range. The content ratio (A) / (B) is 100 / 120-100.
/ 150 (weight ratio). If the ratio (A) / (B) is less than 100/120, the followability will be reduced, and if it exceeds 100/150, the effect of the present invention cannot be obtained due to a cold flow.
It is preferably 100/120 to 100/150, and more preferably 100/120 to 100/130.

Further, as the photopolymerization initiator (C), 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, hexaarylimidazole dimer, 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'-dimethoxy-2-phenylacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, phenylglyoxylate, α-hydroxyisobutylphenone, dibezosparone, 1- (4-isopropylphenyl)- 2-hydroxy-2-methyl-1-
Examples thereof include propanone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, tribromophenylsulfone, and tribromomethylphenylsulfone, and one or more of these are used. At this time, the total blending ratio of the photopolymerization initiator (C) should be about 1 to 20 parts by weight based on 100 parts by weight of the total amount of the base polymer (A) and the ethylenically unsaturated compound (B). Appropriate.

The fluorescent substance (D) is not particularly limited, but is preferably a substance obtained by using a rare earth oxyhalide or the like as a host and activating the host with an activator. ₂ O ₃ : Eu, YVO ₄ : Eu,
(Y, Gd) BO ₃ : Eu (more than red), BaAl ₁₂ O
₁₉ : Mn, Zn ₂ SiO ₄ : Mn, LaPO ₄ : Tb (green or more), BaMgAl ₁₄ O ₂₃ : Eu, BaMgAl ₁₆
O ₂₇ : Eu (more than blue) and the like, and other phosphors include Y ₂ O ₃ S: Eu, γ-Zn ₃ (PO ₄ ) ₂ : M
n, (ZnCd) S: Ag + In ₂ O ₃ (red or more), Z
nS: Cu, Al, ZnS: Au, Cu, Al, (Zn
Cd) S: Cu, Al, Zn ₂ SiO 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 (more green), ZnS: Ag + red pigment, Y ₂ SiO ₃ : Ce (more blue), etc., can be used, and preferably have a specific gravity of 4.0 or more (more preferably 4.0 to 4.0).
8.0) is used.

In the present invention, the method of incorporating the phosphor (D) is not particularly limited, and may be a known method, for example, a predetermined amount of the phosphor (D) may be added to the resin compositions (A) to (C). And then thoroughly mixing and stirring to uniformly disperse the phosphor. In this case, the content of the phosphor (D) is preferably 1 to 50 parts by weight based on 100 parts by weight of the total amount of the base polymer (A) and the ethylenically unsaturated compound (B) in the photosensitive resin composition, More preferably 10-3
0 parts by weight. The photosensitive resin composition of the present invention further includes a dye (coloring and coloring), an adhesion promoter, a plasticizer, an antioxidant, a thermal polymerization inhibitor, a solvent, a surface tension modifier, a stabilizer, and a chain transfer. Additives such as an agent, an antifoaming agent, and a flame retardant can be appropriately added. Production of a laminate for a photoresist film using the photosensitive resin composition containing (A) to (D) of the present invention and a method of forming a phosphor pattern using the laminate will be described.

(Lamination Method) The above-mentioned photosensitive resin composition is applied to a base film surface such as a polyester film, a polypropylene film, or a polystyrene film, and then a polyethylene film or a polyvinyl alcohol-based film is applied from above the coated surface. Or the like to form a laminate for a photoresist film.
At this time, the thickness of the photosensitive resin composition varies depending on the content of the phosphor and the structure of the PDP, and cannot be unconditionally determined, but is usually suitably selected from 10 to 200 μm.

(Exposure) In order to form an image with a photoresist film, an adhesive force between a base film (polyester film, polyvinyl alcohol film, nylon film, cellulose film, etc.) and a photosensitive resin composition layer, and a protective film and a photosensitive film The adhesive strength with the resin composition layer is compared, and the film having the lower adhesive strength is peeled off, and then the photosensitive resin composition layer side is adhered to the PDP substrate. Although a transmissive panel may be used, in order to maximize the effects of the present invention, it is preferable to use a flat substrate for PDP (reflective panel) in which cells are previously formed by glass partition walls. The photoresist film of the present invention is laminated on a flat substrate, and pressed from above with a mold or the like having a convex shape matching the concave shape of the cell. After the photoresist film has been made to follow the shape of the photoresist film, a pattern mask is brought into close contact with the other film and exposed. At this time, if necessary, it is possible to laminate two or more sheets of the photoresist film. When the photosensitive resin composition does not have 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 by ultraviolet irradiation, and as a light source at this 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 resist is peeled off and developed. Since the photosensitive resin composition of the present invention is 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. (Firing) 500-550 of the cell-formed substrate after the above treatment
Firing is performed at ℃ to fix the phosphor inside the cell. In this way, the phosphor can be fixed on the glass substrate. To form a full-color PDP,
It can be manufactured by repeatedly performing the above (exposure) to (firing) using a photoresist film containing each of red, blue and green phosphors.

[0018]

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 (Adjustment of dope) The following base polymer (A) 55
Parts, 70 parts of the following ethylenically unsaturated compound (B), 8 parts of a photoweight initiator (C) having the following formulation, and the following phosphor (D)
50 parts were mixed to prepare a resin composition. Base polymer (A) methyl methacrylate / n-butyl methacrylate / 2
The copolymerization ratio of ethylhexyl acrylate / styrene / methacrylic acid is 32/30/15/2/2 by weight
Copolymer having an acid value of 143.3 and a glass transition point of 6
6.3 ° C, weight average molecular weight 80,000)

Ethylenically unsaturated compound (B) tetraethylene glycol diacrylate / glycerin triacrylate ("OT" manufactured by Daicel UBC, Inc.
A-480 ") 25/10 by weight mixture

Photopolymerization initiator (C) Benzophenone / 4,4'-diethylaminobenzophenone / 2,2-bis (o-chlorophenyl) 4,5
4 ′, 5′-Tetraphenyl-1,2′-biimidazole 8 / 0.15 / 1 by weight mixture phosphor (D) Y ₂ O ₂ S: Eu (emission wavelength: 642 nm, particle size: 2 .2 ± 0.5 μm,
Specific gravity; 5.1)

(Preparation of Dry Film) The above-mentioned dope was applied to a thickness of 2 using an applicator having a gap of 10 mil.
After coating on a 0 μm polyester film and leaving it at room temperature for 1 minute and 30 seconds, it is dried in an oven at 60 ° C., 90 ° C. and 110 ° C. for 3 minutes each to obtain a resist thickness of 70 μm.
(Photoresist film) (however, no protective film is provided). (Lamination on PDP substrate) Glass substrate (200 mm × 2) pre-heated to 60 ° C. in an oven at a partition wall (height: 100 μm, width: 80 μm, slit: 150 μm)
00 mm × 2 mm), the above photoresist film was laminated at a laminating roll temperature of 100 ° C. and a roll pressure of 3 kg / c.
The lamination was performed under the conditions of m ² and lamination speed of 1.0 m / sec. (Exposure, Development) After lamination, a pattern was placed on the entire surface of the polyester film so that the inside of the partition (except on the partition) was exposed, and exposure was performed at 80 mj with an exposure machine manufactured by Oak Manufacturing Co., Ltd. After a hold time of 15 minutes after the exposure, development was carried out in a 1% aqueous solution of Na ₂ CO ₃ at 30 ° C. for 1.5 times the minimum development time. The followability of the photoresist film to the cell at this time was evaluated in the following manner.

[Followability to Cell] Using a part of the glass substrate on which the above-mentioned lamination was formed as a sample, the substrate was cut in a direction perpendicular to the stripe pattern, and the cross section was SEM.
(Scanning electron microscope) and evaluated as follows. ○ −−− No air bubbles are observed at all △ −−− Some air bubbles are seen between the partition walls × −−− Cavities are seen at the bottom of the partition walls and do not follow the lower part of the partition walls (baking) Development Thereafter, it was placed in a firing furnace and heated to about 550 ° C. to burn off the resin, thereby forming a pattern of the phosphor alone. With respect to the obtained fired substrate, the dispersibility of the phosphor was evaluated as follows. [Dispersibility of Phosphor] Using the glass substrate after the baking described above as a sample, the substrate is cut in the direction perpendicular to the stripe pattern, and the filling height of the phosphor in the cross section varies (minimum height to maximum height). Was observed by SEM (scanning electron microscope) and evaluated as follows. ○ −−− 45 to 55 μm △ −−− 40 to 60 μm × −−− 30 to 70 μm

Example 2 A dry film was obtained in the same manner as in Example 1 except that the base polymer (A) was changed to 52 parts and the ethylenically unsaturated compound (B) was changed to 73 parts. Was. Example 3 In Example 1, the ethylenically unsaturated compound (B) was replaced with tetraethylene glycol diacrylate / glycerin triacrylate (“OTA” manufactured by Daicel UBC, Inc.).
-480 ") to obtain a dry film, except that a mixture having a weight ratio of 25/25 was obtained.

Comparative Example 1 A dry film was obtained in the same manner as in Example 1, except that the base polymer (A) was changed to 62 parts and the ethylenically unsaturated compound (B) was changed to 63 parts. Was. Comparative Example 2 A dry film was obtained in the same manner as in Example 1 except that the amount of the base polymer (A) was changed to 45 parts and the amount of the ethylenically unsaturated compound (B) was changed to 80 parts.
Table 1 shows the evaluation results of the examples and the comparative examples.

[0025]

[Table 1]

[0026]

The photoresist film of the present invention contains a base polymer, an ethylenically unsaturated compound and a phosphor, and has a specific ratio of the base polymer and the ethylenically unsaturated compound. A photoresist layer having excellent followability and excellent dispersion stability of the phosphor can be supplied, which is very useful for forming a phosphor of PDP.

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[Procedure amendment]

[Submission date] February 12, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 2 in the claims column

[Correction method] Change

[Correction contents]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction contents]

[0004]

The inventors of the present invention have conducted intensive studies on the conformability of a photoresist film to cells, and as a result, have found that a base film containing an ethylenically unsaturated compound, a phosphor and a base polymer. And the content ratio of the ethylenically unsaturated compound is 100/120 to 100/1
It has been found that a photoresist film obtained by laminating a photosensitive resin composition having a weight ratio of 50 to a base film has excellent followability to cells and excellent dispersibility of a phosphor. Glycerol as a water-soluble unsaturated compound
Effects of the above when using the down acrylate and have completed the present invention found to be more pronounced.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction contents]

As the ethylenically unsaturated compound (B),
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 A polyfunctional monomer such as ether poly (meth) acrylate may be mentioned, and a combination of a bifunctional monomer and a trifunctional monomer is preferred, and a glycerin- modified triacrylate is particularly preferably used as the trifunctional monomer.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction contents]

Ethylenically unsaturated compound (B) tetraethylene glycol diacrylate / glycerin triacrylate (manufactured by Daicel UBC, "OT
A-480 ") 25/10 by weight mixture

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0023

[Correction method] Change

[Correction contents]

Example 2 A dry film was obtained in the same manner as in Example 1 except that the base polymer (A) was changed to 52 parts and the ethylenically unsaturated compound (B) was changed to 73 parts. Was. Example 3 In Example 1, the ethylenically unsaturated compound (B) was replaced with tetraethylene glycol diacrylate / glycerin triacrylate ("OTA" manufactured by Daicel UBC, Inc.).
-480 ") to obtain a dry film, except that a mixture having a weight ratio of 25/25 was obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09K 11/08 C09K 11/08 J

Claims (4)

[Claims] 1. A composition comprising a base polymer, an ethylenically unsaturated compound and a phosphor, wherein the content ratio of the base polymer and the ethylenically unsaturated compound is 100/120 to 100/1.
A photoresist film obtained by laminating a photosensitive resin composition having a weight ratio of 50 to a base film. 2. The method according to claim 1, wherein glycerin triacrylate is used as the ethylenically unsaturated compound.
The photoresist film as described in the above. 3. The content of the phosphor is from 1 to 5 based on 100 parts by weight of the total amount of the base polymer and the ethylenically unsaturated compound.
3. The photoresist film according to claim 1, wherein the amount is 0 parts by weight. 4. The photoresist film according to claim 1, wherein the photoresist film is used as a material for forming a pattern of a phosphor at the time of manufacturing a phosphor display.