JPH0895239A - Photoresist film - Google Patents

Abstract

PURPOSE: To form a photoresist layer excellent in the dispersion stability of a phosphor and to ensure superior pattern forming precision and adhesion to a substrate of glass, etc., by incorporating the phosphor and inorg. powder into a photosensitive resin compsn. and laminating the resultant compsn. on a base film. CONSTITUTION: A phosphor and inorg. powder are incorporated into a photosensitive resin compsn. and the resultant compsn. is laminated on a base film to obtain the objective photoresist film. The photosensitive resin compsn. consists of a base polymer, an ethylenically unsatd. compd. and a photopolymn. initiator. Acrylic resin, polyester resin or polyurethane resin is, e.g. used as the base polymer. The phosphor is not especially limited but a phosphor obtd. by activating a matrix such as oxyhalide of a rare earth element with an activator is preferably used. The inorg. powder is, e.g. glass powder, alumina powder, silica powder, magnesium oxide powder or tin oxide powder, glass powder is preferably used and silicate glass powder is especially important.

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 an inorganic powder, and more specifically, a plasma display panel (PDP), a fluorescent display device, and a hybrid integrated circuit. The present invention relates to a photoresist film that is useful when manufacturing a fluorescent display such as.

[0002]

2. Description of the Related Art Recently, various flat panel displays have been actively developed, and among them, PDPs have attracted attention.
In the future, the application will be expanded from the display screen of a laptop computer to various electronic bulletin boards and further to a so-called "wall TV". The cells of the display panel of the PDP are coated with phosphors for color display, and the phosphors develop color by the ultraviolet rays generated by the enclosed gas in the cells due to the applied voltage. As a method for applying this phosphor, a method in which a slurry liquid of a photoresist in which phosphors of respective colors are dispersed is applied by screen printing (Japanese Patent Laid-Open No. HEI 1
-115027, JP-A-1-124928), a method of pouring the slurry liquid into the cell (JP-A-2-155142), and the like have been tried.

[0003]

However, since all of the above methods use a liquid photoresist, it is necessary to confirm the dispersed state of the phosphor before coating. If a dispersion failure such as the above occurs, re-dispersion processing must be performed. Further, even when the liquid photoresist is stored for a long period of time, the storage stability is lacking due to the promotion of dark reaction and the like, and in any case, the final pattern tends to have variations in brightness, which impairs its commercial value. There is. Further, in the case of a liquid photoresist, the coating thickness is usually 20 μm or less, and it is difficult to apply a large amount of phosphor more than that to improve the coloring effect. It also has the drawback that printing must be repeated and the forming accuracy is poor.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, a photosensitive resin composition containing a phosphor and an inorganic powder is laminated on a base film. Since the photoresist film can always supply the photoresist layer which is excellent in dispersion stability of the fluorescent substance without causing the defective dispersion of the fluorescent substance, it is possible to form a stable pattern without variation in brightness.
A cured resist layer with a thickness of μm or more can be formed, the pattern formation accuracy is superior to the conventional method, and the adhesion to the substrate such as glass is also excellent. Furthermore, the content of the phosphor is in the photosensitive resin composition. 1 to 50 parts by weight based on 100 parts by weight of the total amount of the base polymer and ethylenically unsaturated compound, and 1 to 100 parts by weight of the inorganic powder based on 100 parts by weight of the phosphor, They have found that the effects can be maximized, and have completed the present invention. The present invention is described in detail below.

The photosensitive resin composition used in the present invention is
It comprises a base polymer (A), an ethylenically unsaturated compound (B), and a photopolymerization initiator (C). As the base polymer (A), an acrylic resin, a polyester resin, a polyurethane resin or the like is used. Among these, an acrylic copolymer having (meth) acrylate as a main component and optionally an ethylenically unsaturated carboxylic acid or another copolymerizable monomer is important. An acetoacetyl group-containing acrylic copolymer can also be used.

Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, and 2
-Ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate and the like are exemplified. It

As the ethylenically unsaturated carboxylic acid, monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid are preferably used, and in addition, dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, or their anhydrides. A thing and a half ester can also be used. Among these, acrylic acid and methacrylic acid are particularly preferable. When the dilute alkali developing type is used, ethylenically unsaturated carboxylic acid is contained in an amount of about 15 to 30% by weight (acid value of 100 to 2).
It is necessary to copolymerize (about 00 mgKOH / g).
Examples of other copolymerizable monomers include acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, alkyl vinyl ether and the like.

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 polyglycidyl ether poly (meth ) Examples include polyfunctional monomers such as acrylate. An appropriate amount of a monofunctional monomer may be used together with these polyfunctional monomers.

Examples of monofunctional monomers are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and 2-phenoxy-2-hydroxypropyl (meth) acrylate. , 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate,
Examples thereof include glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, half (meth) acrylate of a phthalic acid derivative, and N-methylol (meth) acrylamide.

The ratio of the ethylenically unsaturated compound (B) to 100 parts by weight of the base polymer (A) is 10 to 20.
It is desirable to select from 0 part by weight, particularly 40 to 100 parts by weight. An insufficient amount of the ethylenically unsaturated compound (B) leads to poor curing, a decrease in flexibility, and a delay in the developing rate. An excessive amount of the ethylenically unsaturated compound (B) increases the tackiness, cold flow, and peeling of the cured resist. This leads to a decrease in speed.

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, p, p′-bis (dimethylamino) benzophenone, p, p′-bis (diethylamino) ) Benzophenone, p, p'-diethylaminobenzophenone, pivaloin ethyl ether, 1,1-dichloroacetophenone, p-t-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
-Propanone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, tribromophenyl sulfone, tribromomethylphenyl sulfone and the like are exemplified. At this time, the total mixing ratio of the photopolymerization initiator (C) is 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 phosphor (D) contained in the photosensitive resin composition of the present invention is not particularly limited,
It is preferable to use a rare earth oxyhalide or the like as a base material and activate the base material with an activator. For example, as the ultraviolet excitation type phosphor, Y ₂ O ₃ : Eu, YVO ₄ : Eu, (Y, G
d) BO ₃ : Eu (above red), Zn ₂ GeO ₂ : Mn,
BaAl ₁₂ O ₁₉ : Mn, Zn ₂ SiO ₄ : Mn, LaPO
₄ : Tb (above green), Sr ₅ (PO ₄ ) ₃ CI: Eu, B
aMgAl ₁₄ O ₂₃ : Eu ²⁺ , BaMgAl ₁₆ O ₂₇ : Eu
(Above blue) and the like. Other phosphors include
Y ₂ O ₃ S: Eu, γ-Zn ₃ (PO ₄ ) ₂ : Mn, (Zn
Cd) S: Ag + In ₂ O ₃ (above red), ZnS: C
u, Al, ZnS: Au, Cu, Al, (ZnCd)
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 (above green), ZnS: Ag + red pigment,
Y ₂ SiO ₃ : Ce (above blue) or the like can be used, and it is of course possible to blend two or more kinds.

Further, examples of the inorganic powder (E) contained in the photosensitive resin composition of the present invention include glass powder, alumina powder, silica powder, magnesium oxide powder, tin oxide powder and indium tin oxide powder. Among them, glass powder is preferable, and silicate glass powder is particularly important. The particle diameter of the powder (E) is preferably from 2 to 10 μm, more preferably from 2 to 5 μm, and when the particle diameter is larger than 10 μm, the brightness is lowered, and conversely 2 μm.
If it is smaller than this, the effect of adding the powder is reduced, which is not preferable.

The method of incorporating the phosphor (D) and the inorganic powder (E) into the photosensitive resin composition of the present invention is not particularly limited, and a known method such as the above-mentioned photosensitive resin composition containing a predetermined amount of fluorescent light is used. There is a method in which the body (D) and the inorganic powder (E) are added, and the mixture is sufficiently mixed and stirred to uniformly disperse the phosphor (D) and the inorganic powder (E). In this case, the content of the phosphor (D) is 1 based on the total amount of the base polymer (A) and the ethylenically unsaturated compound (B) in the photosensitive resin composition.
The amount is preferably 1 to 50 parts by weight, more preferably 10 to 30 parts by weight, relative to 00 parts by weight. When the content of the phosphor (D) exceeds 50 parts by weight, it becomes difficult to form a dry film, and when it is less than 1 part by weight, the fluorescence emission intensity (luminance) tends to decrease, which is not preferable. Further, the content of the inorganic powder (E) is preferably 1 to 100 parts by weight, more preferably 1 part by weight, relative to 100 parts by weight of the phosphor (D).
-50 parts by weight, especially 1-20 parts by weight are preferred. If the content of the powder (E) exceeds 100 parts by weight, the fluorescence emission intensity (luminance) will decrease, and if it is less than 1 part by weight, the effect of addition tends to be poor, such being undesirable.

In addition to the photosensitive resin composition containing the phosphor (D) and the inorganic powder (E) of the present invention, dyes (coloring and coloring), adhesion promoters, plasticizers, antioxidants, and heat Additives such as a polymerization inhibitor, a solvent, a surface tension modifier, a stabilizer, a chain transfer agent, a defoaming agent, and a flame retardant can be appropriately added. Manufacturing of Dry Film Resist Laminate (Photoresist Film) Using Photosensitive Resin Composition Containing Phosphor (D) and Inorganic Powder (E) of the Present Invention and Method of Forming Phosphor Pattern Using the Same explain.

(Layering method) A photosensitive resin composition containing the above-mentioned phosphor (D) and inorganic powder (E) is applied to the surface of a base film such as a polyester film, a polypropylene film or a polystyrene film, and then applied. A protective film such as a polyethylene film or a polyvinyl alcohol film is coated on the work surface to form a dry film resist laminate. The film thickness of the photosensitive resin composition at this time varies depending on the contents of the phosphor (D) and the inorganic powder (E) and the structure of the PDP, etc., and cannot be generally stated, but it is usually from 10 to 200 μm. It is preferably selected.

(Exposure) In order to form an image with a dry film resist, the adhesive strength between the base film and the photosensitive resin composition layer and the adhesive strength between the protective film and the photosensitive resin composition layer are compared and the adhesion is performed. After peeling off the film having the lower force, the side of the photosensitive resin composition layer is attached to the anode fixing surface of the front glass, for example, in the case of a PDP using a transmission type panel, and then the other side. A pattern mask is brought into close contact with the film for exposure. At this time, if necessary,
It is also possible to laminate two or more dry film resists. Further, 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 done by UV irradiation,
At that time, as a 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 irradiation with ultraviolet rays, heating can be performed as necessary to achieve complete curing.

(Development) After exposure, the film on the resist is peeled off and developed. Since the photosensitive resin composition of the present invention is a dilute alkali developing type, the development after exposure is
1-2% by weight of alkali such as sodium carbonate and potassium carbonate
Perform using a dilute aqueous solution. (Firing) The cell-formed substrate after the above treatment is 500 to 550 ° C.
Is baked to fix the phosphor (D) inside the cell. In this way, the phosphor (D) can be fixed on the glass substrate. In order to form a full color PDP, red, blue and green phosphors (D) are used.
It can be produced by repeating the above (exposure) to (baking) using a photoresist film containing a.

Further, it is also possible to fix the phosphor (D) to the flat substrate for PNP in which the cells are previously formed by the glass partition walls by using the photoresist film of the present invention (reflection type panel). For example, the photoresist film of the present invention was laminated on the flat substrate for PDP, and pressed from above with a mold or the like having a convex shape that matches the concave shape of the cell, and the photoresist film was made to follow the cell shape. After that, the phosphor (D) can be fixed inside the cell by the above steps of (exposure) to (baking). At this time, since flexibility is required for the photoresist film, it is preferable to use a flexible film such as polyvinyl alcohol, nylon, or cellulose as the base film or the protective film.

[0020]

Since the photoresist film of the present invention uses the photosensitive resin composition containing the phosphor and the inorganic powder, the photoresist layer does not cause the dispersion failure of the phosphor and is always excellent in the dispersion stability of the phosphor. , A cured resist layer having a thickness of 10 μm or more is formed, the pattern forming accuracy is superior to that of the conventional method, and the adhesiveness to a substrate such as glass is also excellent. Very useful for pattern formation.

[0021]

EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, "%" and "parts" mean weight basis unless otherwise specified. Example 1 (Preparation of dope) 46 parts of the following base polymer (A),
54 parts of the following ethylenically unsaturated compound (B), 8 parts of the following photopolymerization initiator (C), 26 parts of the following phosphor (D) and 1.3 parts of inorganic powder (E) (phosphor (D ) 5 parts) was mixed with 100 parts to prepare a resin composition. Base polymer (A) methyl methacrylate / n-butyl methacrylate / 2
-A copolymer in which the copolymerization ratio of ethylhexyl acrylate / methacrylic acid is 55/8/15/22 on a weight basis (acid value 143.3, glass transition point 66.3 ° C, weight average molecular weight 80,000).

The mixture light weight 20/10/6 ethylenically unsaturated compound (B) trimethylolpropane triacrylate / polyethylene glycol (600) dimethacrylate / ethylene oxide-modified phthalic acid acrylate (manufactured by Kyoeisha Yushi Kogyo Co., Ltd.) Polymerization initiator (C) benzophenone / p, p′-diethylaminobenzophenone / 2,2-bis (o-chlorophenyl) 4,5,
4 ', 5'-tetraphenyl-1,2' mixture phosphor bicycloalkyl weight ratio 8 / 0.15 / 1 imidazole (D) (Y, Gd) BO 3: Eu / Zn 2 SiO 4: Mn / Ba
MgAl ₁₄ O ₂₃ : Eu ²⁺ = 33/50/17 (weight ratio)
Blend (average particle size: 4 ± 2μm)

Inorganic powder (E) Glass powder (silicate glass, particle size; 3 ± 0.5 μm,
Specific gravity: 6.5) (Preparation of dry film)
Using a mill applicator, coat on a polyester film having a thickness of 20 μm, leave it at room temperature for 1 minute 30 seconds, and then in an oven at 60 ° C., 90 ° C., 110 ° C.
The film was dried for 1 minute to give a dry film having a resist thickness of 20 μm (however, no protective film was provided). (Lamination on glass substrate) This dry film
Glass substrate preheated to 60 ° C in an oven (thickness 0.1
IT with a conductive circuit of about 0.2 μm formed on the surface
O film substrate, 200 mm x 200 mm x 2 mm), laminated roll temperature 100 ° C, same roll pressure 3 kg / cm
^2. Lamination was performed at a laminating speed of 1.5 m / sec.

(Exposure, development) After laminating, 20
The resist surface was exposed to 40 mj with a 3 kW ultra-high pressure mercury lamp using an exposure machine HMW-532D manufactured by Oak Manufacturing Co., Ltd. on the resist surface so as to form an exposed portion having a pitch of 0 μm square and up / down / left / right 260 μm pitch. After a hold time of 15 minutes after exposure, development was carried out at 20 ° C. using a 1% Na ₂ CO ₃ aqueous solution for 1.5 times the minimum development time. (Baking) In the baking oven after development, from room temperature to 550 ° C 1
The resin content was burned up by raising the temperature over time. The evaluation details and the evaluation criteria are shown below.

A. Luminance A PDP panel was produced using the above-mentioned glass substrate, and the luminance of the phosphor portions at the four corners and the center at a total of 5 places was measured with a spot luminance meter, and the variation and the average luminance were examined. b. Storage stability The above dry film is left for 1 month in the dark at 40 ° C. and 60% RH, and then the same (laminating on a glass substrate) to (baking) as described above is performed, and variations in brightness and average brightness are similarly performed. I checked. c. Adhesion About 1kg / by air spray on the phosphor pattern after firing
The adhesion of the phosphor was examined by blowing air at a pressure of cm ² . The evaluation criteria are as follows. ○ −−− Almost no scattering of the phosphor is observed. × −−− Phosphors are scattered and hardly remain on the substrate.

Examples 2 and 3 As shown in Table 1, the same evaluation as in Example 1 was carried out by changing the content of the inorganic powder (E). Comparative Example 1 Evaluation was performed in the same manner as in Example 1 except that the inorganic powder (E) was not added. Comparative Example 2 In Example 1, the dope was directly applied to the glass substrate (resist thickness 20 μm) without forming a dry film to form a phosphor pattern in the same manner as in Example 1, and the same evaluation was performed. went. Table 2 shows the evaluation results of Examples and Comparative Examples.
Shown in.

[0027]

[Table 1] * Parts by weight relative to 100 parts by weight of phosphor (D).

[0028]

[Table 2] Item a Item b Item c Item Variance Average Variance Average Example 1 3 30 3 30 ○ Example 2 4 29 29 29 ○ Example 3 3 30 3 30 ○ Comparative Example 1 5 25 5 23 × Comparative Example 2 15 22 20 18 ○ Note: The variations in the above a and b items represent the difference between the maximum and minimum values of the measured values at 5 points respectively, and the average means the average value of the measured values at 5 points respectively. Is cd / m ² .

[0029]

Since the photoresist film of the present invention uses the photosensitive resin composition containing the phosphor and the inorganic powder, it does not cause poor dispersion of the phosphor and is always excellent in dispersion stability of the phosphor. A photoresist layer can be supplied, a cured resist layer with a thickness of 10 μm or more can be formed, patterning accuracy is superior to conventional methods, and adhesion to a substrate such as glass is also excellent. It is very useful for forming phosphor patterns.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09K 11/78 CPL 9280-4H G03F 7/028 7/033 H01J 9/227 C

Claims (4)

[Claims] 1. A photoresist film comprising a base film and a photosensitive resin composition containing a phosphor and an inorganic powder. 2. The total content of the phosphor and the base polymer and the ethylenically unsaturated compound in the photosensitive resin composition is 100.
2. The photoresist film according to claim 1, wherein the content of the inorganic powder is 1 to 50 parts by weight and the content of the inorganic powder is 1 to 100 parts by weight with respect to 100 parts by weight of the phosphor. 3. The inorganic powder is at least one selected from glass powder, alumina powder, silica powder, magnesium oxide powder, tin oxide powder and indium tin oxide powder.
The photoresist film according to claim 1, wherein the photoresist film is a seed. 4. The photoresist film according to claim 1, which is used as a material for forming a pattern of a phosphor when a phosphor display is manufactured.