JPH0895250A - Photoresist film - Google Patents

Abstract

PURPOSE: To form a photoresist layer excellent in dispersion stability without causing defective dispersion of a phosphor and to improve the adhesion of the phosphor by incorporating a specified silane compd. and the phosphor into a photosensitive resin compsn. and laminating the resultant compsn. on a base film. CONSTITUTION: A phosphor and at least one kind of silane compd. selected from among epoxysilane, aminosilane and chloropropylsilane are incorporated into a photosensitive resin compsn. and the resultant compsn. is laminated on a base film to obtain the objective photoresist film. 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. Epoxysilane such as γ-glycidoxy-propyltrimethoxysilane or γ-glycidoxypropyltriethoxysilane is especially preferably used as the silane compd. Two or more kinds of such silane compds. may be used in combination.

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 a silane compound, and more specifically, a plasma display panel (PDP), a liquid crystal display device, a fluorescent display. The present invention relates to a photoresist film useful in manufacturing a fluorescent display such as a device or a hybrid integrated circuit.

[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. Furthermore, with a liquid photoresist, the coating thickness is usually at most about 20 μm, and it is impossible to improve the color development effect by applying a large amount of phosphor more than that. Printing of the resist has to be repeated, and there is a drawback that the forming accuracy is poor.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have laminated a photosensitive resin composition containing a phosphor and a silane compound on a base film. The resulting photoresist film can always supply a photoresist layer having excellent dispersion stability of the phosphor without causing poor dispersion of the phosphor, so that it is possible to form a stable pattern without variations in brightness, and 10 μm It is possible to form the above-mentioned cured resist layer, the patterning accuracy is superior to the conventional method, and the adhesiveness to the substrate such as glass is also excellent, and further, the content of the phosphor is in the photosensitive resin composition. When the content of the silane compound is 1 to 50 parts by weight and the content of the silane compound is 0.1 to 3 parts by weight, based on 100 parts by weight of the total amount of the base polymer and the ethylenically unsaturated compound, the effect of the present invention is maximized. It found that you can, 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, 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,
It is also possible to use Y ₂ SiO ₃ : Ce (above blue) or the like.

Furthermore, in the present invention, at least one silane compound (E) selected from epoxysilane, aminosilane and chloropropylsilane contained in the above-mentioned photosensitive resin composition is γ-glycidoxypropyltrimethoxy. Silane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, Epoxysilanes such as β- (3,4-epoxycyclohexyl) -ethyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane , N-β (aminoethyl) γ-aminopropylmethyldimethoxy Emissions, N-beta (aminoethyl) .gamma.-aminopropyl methyl diethoxy silane, gamma
-Aminopropyltriethoxysilane, N-phenyl-
Aminosilanes such as γ-aminopropyltrimethoxysilane and chloropropylsilane such as γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropylmethyldimethoxysilane and γ-chloropropylmethyldiethoxysilane. Among them, γ-glycidoxypropyltrimethoxysilane, γ
-Epoxysilanes such as glycidoxypropyltriethoxysilane are preferable, and two or more kinds of the silane compounds can be used in combination.

The method of incorporating the phosphor (D) and the silane compound (E) into the photosensitive resin composition of the invention is as follows:
The method is not particularly limited, and a known method, for example, a predetermined amount of the phosphor (D) and the silane compound (E) is added to the above-mentioned photosensitive resin composition, and the mixture is sufficiently stirred to mix the phosphor (D) and the phosphor (D). There is a method of uniformly dispersing the silane compound (E). The content of the phosphor (D) in this case 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, It is more preferably 10 to 30 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.

The content of the silane compound (E) is 0.1 to 100 parts by weight of the total amount of the base polymer (A) and the ethylenically unsaturated compound (B) in the photosensitive resin composition. 3 parts by weight is preferable, and more preferably 0.5 part.
~ 1 part by weight. When the content of the compound (E) exceeds 3 parts by weight, the adhesiveness to the phosphor decreases, and when it is less than 0.1 parts by weight, the effect of addition is small and it is not preferable. In addition to the photosensitive resin composition containing the phosphor (D) of the present invention and the silane compound (E), dyes (coloring and coloring), adhesion promoters, plasticizers, antioxidants, thermal polymerization Additives such as inhibitors, solvents, surface tension modifiers, stabilizers, chain transfer agents, defoamers and flame retardants can be added as appropriate. The phosphor of the present invention (D) and the silane compound (E)
A method for producing a laminate for a dry film resist (photoresist film) using a photosensitive resin composition containing and a method for forming a phosphor pattern using the same will be described.

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

(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 PDP in which cells are formed in advance by glass partition walls, 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 a photosensitive resin composition containing a phosphor and a silane compound, it is a photoresist having excellent dispersion stability of the phosphor without causing dispersion failure of the phosphor. A layer can be supplied, a cured resist layer with a thickness of 10 μm or more is formed, the pattern formation accuracy is superior to the conventional method, and the adhesion to a substrate such as glass is also excellent. It is very useful for forming phosphor patterns during the manufacture of display tubes and the like.

[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 photogravimetric initiator (C) having the following formulation, 26 parts of the following phosphor (D) and 0.75 part of the silane compound (E) were mixed. A resin composition was prepared. 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)

Silane-based compound (E) γ-glycidoxypropyltrimethoxysilane (molecular weight: 236.3, specific gravity 1.07) (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 allowed to stand for 1 month in the dark at 40 ° C. and 60% RH, and then (lamination on a glass substrate) to (baking) is carried out in the same manner as above to obtain the variation in brightness and the average brightness. Examined. c. The phosphor pattern (200 μm square) after the adhesive firing was observed with an SEM (scanning electron microscope) to examine the height (μm) of the edge (corner) of the phosphor pattern lifted from the glass substrate. The evaluation criteria are as follows. ◎ --- No lift is observed at all ○ --- Lifting height is less than 10 μm × --- Lifting height is 10 μm or more

Examples 2 and 3 In Example 1, the amount of γ-glycidoxypropyltrimethoxysilane added was changed to 0.5 parts (Example 2) and 1 part (Example 3). The same evaluation as in 1 was performed. Example 4 The same evaluations as in Example 1 were carried out except that in Example 1, γ-glycidoxypropyltrimethoxysilane was used instead of γ-glycidoxypropyltrimethoxysilane.

Comparative Example 1 The same evaluations as in Example 1 were carried out except that γ-glycidoxypropyltrimethoxysilane was not added in Example 1. Comparative Examples 2 to 5 In Example 1, instead of γ-glycidoxypropyltrimethoxysilane, vinylethoxysilane (Comparative Example 2), γ-mercaptopropyltrimethoxysilane (Comparative Example 3), isopropyltriisostearoyl titanate ( Example 1 except that Comparative Example 4) and acetoalkoxyaluminum diisopropylate (Comparative Example 5) were used.
The same evaluation as was done. Table 1 shows the evaluation results of the examples and comparative examples.

[0028]

[Table 1] Item a Item b Item c Item Variance Average Variance Average Example 1 3 30 3 30 ◎ Example 2 3 3 30 3 29 ○ Example 3 5 28 4 29 ○ Example 4 4 30 4 29 ◎ Comparative Example 1 5 25 5 23 × Comparative Example 2 10 14 8 10 × Comparative Example 3 13 10 13 11 × Comparative Example 4 Adhesiveness was extremely poor and luminance could not be measured × Comparative Example 5 Adhesiveness was extremely poor and luminance could not be measured × Note: The above-mentioned variations in items a and b are the difference between the maximum and minimum values of the measured values at each of the five points, and the average is the average value of the measured values at the five points, and these units are cd / m. ^{Is 2} .

[0029]

Since the photoresist film of the present invention uses a photosensitive resin composition containing a phosphor and a specific silane compound, the dispersion stability of the phosphor is always maintained without causing poor dispersion of the phosphor. It is possible to supply an excellent photoresist layer, the adhesiveness of the phosphor is excellent, and the thickness of the cured resist can be freely set to 10 to 200 μm. Therefore, manufacturing of PDP, VFD (fluorescent display tube), etc. It is very useful for the purpose of forming fluorescent substance patterns.

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Claims (3)

[Claims] 1. A photoresist comprising a base film and a photosensitive resin composition containing at least one silane-based compound selected from epoxysilane, aminosilane and chloropropylsilane and a phosphor. the film. 2. The total content of the phosphor and the base polymer and the ethylenically unsaturated compound in the photosensitive resin composition is 100.
The photoresist film according to claim 1, wherein the content of the silane-based compound is 0.1 to 3 parts by weight with respect to 1 part by weight. 3. The phosphor according to claim 1, which is used as a pattern forming material for a phosphor when a phosphor display is manufactured.
The described photoresist film.