JPH11352689A - Photosensitive resin composition for microfabrication, and method for forming rib pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin composition for micro-fabrication without deteriorating insulation characteristics and light emitting luminance by incorporating a polymer specified in an alkali content as an essential component. SOLUTION: This photosensitive composition is composed essentially of the polymer having an alkali content of <=200 ppm. It is preferred that in addition to (a) this polymer, (b) a monomer having at least one ethylenially unsaturated group, such as methyl acrylate or methyl methacrylate, oligomers each having an average molecular weight <=3000 or prepolymer, and (c) a photopolymerization initiator in the case of processing an insulation material by using this photosensitive resin composition. This polymer (b) component is added in an amount of 10-100 weight %, preferably, 10-70 weight % of the total solid of this photosensitive resin composition, and the initiator (c) component is added, preferably, in an amount of 0.1-20 weight % of the (b) component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition, and more particularly, to a fine processing photosensitive resin composition containing a polymer having an alkali content of 200 ppm or less as a main component, and a rib pattern using the same. A method for forming the same.

[0002]

2. Description of the Related Art In recent years, various display devices such as semiconductor devices, liquid crystals, and plasma display panels have been improved in accuracy.
Fine processing by lithography using a photosensitive resin composition is performed for the processing. In the microfabrication method using the lithography, for example, a rib forming layer is provided on a substrate, and a photosensitive resin layer is laminated thereon, as seen in the manufacture of a plasma display panel (hereinafter, referred to as PDP).
It is a processing method such as irradiating an actinic ray through a mask pattern and developing, and performing a sandblasting process on the obtained pattern as a protective film. The PDP is manufactured by firing ribs having cells and lines formed by the sandblasting process, providing a phosphor layer and an electrode layer between the cell structures and the lines, and filling a discharge gas.

[0003]

However, when fine processing by a lithography technique is performed using a conventional photosensitive resin composition, the insulating properties of the insulating material are reduced. In particular, in the formation of the PDP ribs, in addition to the decrease in the insulating properties, the emission luminance also decreased.

In order to solve such problems, the present inventors have conducted intensive studies. As a result, the decrease in the insulating properties of the insulating material is caused by the alkali contained in the polymer used as a binder in the photosensitive resin composition, particularly sodium. Was found to be due to. The inventors have found that by setting the alkali content in the polymer to 200 ppm or less, it is possible to obtain an insulating material without a decrease in insulating properties, and completed the present invention. Ie

According to the present invention, an alkali content of 200 ppm
It is an object of the present invention to provide a photosensitive resin composition for fine processing which contains the following polymer as a main component and does not lower insulation properties or emission luminance.

Another object of the present invention is to provide a method for forming a rib pattern using the photosensitive resin composition for fine processing.

[0007]

SUMMARY OF THE INVENTION In order to achieve the above object, the present invention provides a photosensitive resin composition for fine processing containing a polymer having an alkali content of 200 ppm or less as a main component, and the formation of a rib pattern using the same. According to the method.

The photosensitive resin composition for fine processing of the present invention comprises
As described above, a polymer having an alkali content of 200 ppm or less is contained as a main component. The polymer acts as a binder for the photosensitive resin composition, and specific examples thereof include commercially available polyvinyl alcohol, polyvinyl pyrrolidone, and 70 to 99. % Partially saponified polyvinyl acetate, 70-9
Lower (ac 1-4) acetalized product by formalization or butyralization of 9% partially saponified polyvinyl acetate, 70-99% partially saponified polyvinyl acetate with p-benzaldehyde sulfonic acid, β-butyraldehyde sulfonic acid , O-benzaldehyde sulfonic acid, acetalized product with 2,4-benzaldehyde sulfonic acid, vinyl acetate and ethylene, acrylates, methacrylates,
Copolymers with unsaturated carboxylic acids such as acrylamides, acrylic acid and methacrylic acid, and cationic monomers such as dimethylaminoethyl methacrylate and vinyl succinimide; partially saponified products of these copolymers; and partially stilbazolium group-containing sakenes Polyvinyl acetate, acrylamide, methylenebisacrylamide, N-vinyl acetate,
(Meth) acrylamide-based polymers such as methylolacrylamide, diacetoneacrylamide, triacrylformal, hydroxymethyldiacetoneacrylamide, N, N-diacrylamidedimethylether and methacrylamide, cellulose derivatives, (meth) acrylic acid and the like. Copolymers with (meth) acrylic acid esters and the like, and mixtures thereof can be mentioned. 200 ppm alkali content of the polymer
Purification using an ion exchange resin or the like is suitable for the following.

In processing an insulating material using the photosensitive resin composition for microfabrication, in addition to (a) the polymer having an alkali content of 200 ppm or less, (b) at least one ethylenically unsaturated group And a photopolymerization initiator (c). By containing these components, high-precision fine processing can be easily performed, and the insulating properties of the insulating material do not deteriorate. The component (b) includes methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate,
-Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, ethylene glycol monomethyl ether acrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl ether methacrylate, ethylene glycol diacrylate, ethylene glycol Dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate,
Tetraethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, glycerol acrylate, glycerol methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, Tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipen Dipentaerythritol dimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1,6
Examples include at least one monomer such as hexanediol diacrylate, benzyl acrylate, benzyl methacrylate, and cardo epoxy diacrylate, or an oligomer or prepolymer having an average molecular weight with an upper limit of about 3000. The component (b) is used in an amount of 1 part by weight based on 100 parts by weight of the total solid content of the photosensitive resin composition for fine processing.
It is good to contain in the range of 0 to 100 parts by weight, preferably 10 to 70 parts by weight.

As the component (c), a known photopolymerization initiator can be used and is not particularly limited. Specific examples include benzophenone, 4,4'-bis (dimethylamino) benzophenone, and 3,3-dimethyl- Benzophenone derivatives such as 4-methoxy-benzophenone, anthraquinone,
-Methylanthraquinone, 2-ethylanthraquinone,
anthraquinone derivatives such as tert-butylanthraquinone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin alkyl ether derivatives such as benzoin propyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone; 2-hydroxy-2-methylpropiophenone, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-
Acetophenone derivatives such as methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone; thioxanthone derivatives such as 2-chlorothioxanthone, diethylthioxanthone, isopropylthioxanthone and diisopropylthioxanthone; benzyl;
2,4,6- (trihalomethyl) -s-triazine, 2
-(O-chlorophenyl) -4,5-diphenylimidazolyl dimer, 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, 1,5-bis (9-acridinyl) pentane, 1,3- Bis (9-acridinyl) propane, dimethylbenzylketal, trimethylbenzoyldiphenylphosphine oxide, tribromomethylphenylsulfone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-
1-one, Irgacure (trade name, manufactured by Ciba Geigy)
And the like, but are not limited thereto. Component (c) is added in an amount of 0.1 to 100 parts by weight of component (b).
The content is preferably in the range of 範 囲 20 parts by weight.

When the above-mentioned photosensitive resin composition for fine processing is used particularly for processing a PDP rib, the photosensitive resin composition contains (d) a diazo compound and (e) a polymer emulsion in addition to the component (a). Is good. The component (d) acts as a photo-crosslinking agent for the components (a) and (e) and helps to form a pattern with good resolution, and the component (e) is a solvent that penetrates the surface of the rib-forming layer. And prevent its deterioration. As described above, the photosensitive resin composition for rib processing of the present invention has good adhesiveness to the substrate and has no solvent permeation to the surface of the rib forming layer. The insulating material thus used does not cause a decrease in insulation characteristics or a decrease in light emission luminance. As the component (d), specifically, 4-diazodiphenylamine sulfate, 4-diazodiphenylamine phosphate, 3-methoxy-4-diazodiphenylamine sulfate, 4,4′-diadiazodiphenylamine, 2,2 ′ -Diadiazofluorene, 2-dimethylamino-2'-diazofluorene, 3-methoxy-4-diazodiphenylamine phosphate and the like, and condensates of paraformaldehyde or 4,4'-dimethoxydiphenyl ether. The component (d) is preferably contained in the range of 0.1 to 20 parts by weight based on 100 parts by weight of the component (e).

The component (e) includes polyvinyl acetate, vinyl acetate / ethylene polymer, vinyl acetate / acrylate copolymer, styrene / butadiene polymer,
Methyl methacrylate / butadiene copolymer, acrylonitrile / butadiene copolymer, chloroprene copolymer,
Polymer emulsions of isoprene copolymer, poly (meth) acrylic acid, polyvinyl chloride, polyvinylidene chloride, polystyrene, silicone resin, polyethylene, polyurethane, fluororesin, etc., preferably having an average particle size of 1 to 10 μm A range of polymer emulsions is preferred. When the average particle size of the polymer emulsion is less than 1 μm, the solvent easily penetrates into the surface of the rib-forming layer, and the average particle size is 1 μm.
If it exceeds 0 μm, it may be difficult to form a fine line pattern.

The component (e) is contained in an amount of 20 to 90 parts by weight, preferably 50 to 80 parts by weight, based on 100 parts by weight of the total solid content of the photosensitive resin composition for fine processing.
If the content of the component (e) is less than 20 parts by weight, the solvent may penetrate into the surface of the rib-forming layer, and if it exceeds 90 parts by weight, the peelability of the resist deteriorates.

The photosensitive resin composition for fine processing of the present invention comprises:
Dissolve it in water or an organic solvent and apply it directly to the surface to be processed using an applicator, bar coater, wire bar coater, roll coater, curtain flow coater, or the like, or prepare the prepared photosensitive resin composition with flexibility. It is formed on the photosensitive resin layer by a method such as coating on a support film, disposing a release film on the support film to form a dry film, and bonding the dry film to a surface to be processed. The photosensitive resin layer is then exposed to actinic rays through a mask pattern and exposed,
It is developed to form a fine pattern protective film. By spraying a blast material on the protective film, fine processing can be performed well. As the flexible support film of the dry film, a film having a thickness of 15 to 125 μm is preferable because it is a layer supporting the photosensitive resin layer. Specific examples of the film include a synthetic resin film such as polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, and polyvinyl chloride. Especially polyethylene terephthalate (PET)
Films are preferred in terms of flexibility and waist. Further, the release film is preferably a film which stably protects the photosensitive resin composition layer when not used, but which can be easily peeled off when used. Examples of the release film include films of PET, polyethylene, polypropylene, etc., which have a thickness of 15 to 1 coated or baked with silicone.
A PET film, a polypropylene film, a polyethylene film or the like having a thickness of about 25 μm is suitable. The thickness of the photosensitive resin composition layer is not less than 20 μm in terms of the thickness after drying, but is preferably in the range of 23 to 50 μm in forming the rib pattern. If the film thickness after drying is smaller than the above range, the resistance during processing is poor, and it is difficult to form a highly accurate pattern, which is not preferable.

Next, a specific example of a method for producing a PDP using the photosensitive resin composition for fine processing of the present invention will be described.

(I) Formation of Rib Forming Layer A paste in which an inorganic powder and a vehicle are dispersed is applied on a base material such as glass and dried to form a rib forming layer. Examples of the inorganic powder include lead borate glass, zinc borate glass and the like, Si, B, Pb, Na, K, Mg, Ca, Ba, T
Glasses composed of various oxides such as i, Zr, Al, etc., cobalt oxide, iron oxide, chromium oxide, nickel oxide, copper oxide, manganese oxide, neodymium oxide, vanadium oxide,
Cerium oxide, chipeque yellow, cadmium oxide, alumina, silica, magnesia, spinel, Y ₂ SiO ₅ :
Ce, CaWO ₄ : Pb, BaMgAl ₁₄ O ₂₃ : Eu,
ZnS: (Ag, Cd), Y ₂ O ₃ : Eu, Y ₂ SiO ₅ :
Eu, Y ₃ Al ₅ O ₁₂ : Eu, Zn ₃ (PO ₄ ) ₂ : Mn,
YBO ₃ : Eu, (Y, Gd) BO ₃ : Eu, GdB
O ₃ : Eu, ScBO ₃ : Eu, LuBO ₃ : Eu, Zn ₂
SiO ₄ : Mn, BaAl ₁₂ O ₁₉ : Mn, SrAl ₁₃ O
_{19: Mn, CaAl 12 O 19} : Mn, YBO 3: Tb, B
aMgAl ₁₄ O ₂₃ : Mn, LuBO ₃ : Tb, GdB
O ₃ : Tb, ScBO ₃ : Tb, Sr ₆ Si ₃ O ₃ Cl ₄ : E
u, ZnO: Zn, ZnS: (Cu, Al), ZnS:
Ag, Y ₂ O ₃ S: Eu, ZnS: Zn, (Y, Cd) B
Fluorescent substances such as O ₃ : Eu, BaMgAl ₁₂ O ₂₃ : Eu,
Iron, nickel, copper, aluminum, silver, conductive particles such as silver, gold and the like, and as the vehicle, cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylcellulose, ethylhydroxyethylcellulose, carboxymethylethylcellulose and the like Examples include a polymer compound and a linear (meth) acrylic copolymer.

(Ii) Formation of Rib Defining Pattern After applying the photosensitive resin composition for fine processing to the rib forming layer or forming the photosensitive resin composition layer with a dry film, a predetermined mask pattern was provided. The mask is brought into close contact with the mask pattern and irradiated with actinic rays to expose it.
Develop to form rib definition mask pattern. A blast material is sprayed on the obtained rib definition mask pattern, and the exposed portion is selectively ground and removed to form a rib pattern such as a barrier rib or a priming rib. As the blast material to be used, glass beads, SiC, SiO ₂ ,
1 to 50 of Al ₂ O ₃ , ZrO ₂ , organic plastic material, etc.
Fine particles of about 0 μm can be mentioned. The photosensitive resin composition layer remaining in the sandblasting treatment is removed with a stripping solution. As the stripping solution, a stripping solution such as sodium hydroxide, potassium hydroxide, periodic acid, sodium periodate, or an organic alkali is used. No.

(Iv) Manufacture of PDP The substrate on which the above-mentioned rib pattern is formed is fired at a temperature of 500 ° C. or more to obtain ribs. Then, a phosphor layer or an electrode layer is provided in the cell or between the lines, and discharge is performed. PD with gas
P.

[0019]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0020]

Example 1 An ion exchange resin (manufactured by Organo Co., Ltd.) was added to 100 parts by weight of a 15% by weight aqueous solution of PVA (manufactured by Nippon Synthetic Chemical: T-350, carboxyl group-modified polyvinyl alcohol, Na content: 0.18% by weight). : 10 parts by weight of Amberlite)
After mixing for 12 hours, the mixture was filtered through a 250-mesh filter to obtain a PVA aqueous solution having a sodium content of 80 ppm.

Example 2 Water-soluble cellulose (manufactured by Shin-Etsu Chemical Co., Ltd .: Metroze 60)
10 parts by weight of an ion exchange resin (manufactured by Organo: Amberlite) is added to 100 parts by weight of a 15% by weight aqueous solution containing SH and Na (0.16% by weight), mixed for 12 hours, and then filtered through a 250 mesh filter. By removing water from the cellulose solution obtained by evaporator,
Powdered cellulose having a sodium content of 50 ppm was obtained.

Next, a photosensitive resin composition for fine processing was prepared as follows. (1) Ethylene glycol monoethyl ether diluted solution of the above powdered cellulose (solid content concentration: 10% by weight) 150 parts by weight (2) 3L which is a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name, Shin-Nakamura) (3) sodium borosilicate glass powder 67 parts by weight (4) Irgacure 651 (trade name, manufactured by Ciba Geigy) 3 parts by weight was well kneaded with a three-roll mill.

Next, the prepared photosensitive resin composition for fine processing is applied on a PDP substrate so that the film thickness after drying becomes 150 μm, and dried at 80 ° C. for 1 hour to obtain a 80 μm line / 220 μm space. Exposure was performed by irradiating with an energy amount of 300 mJ / cm ² by an ultra-high pressure mercury lamp through a negative mask. Thereafter, the film was spray-developed with warm water of 40 ° C. for 120 seconds, washed with water, and dried at 80 ° C. for 10 minutes to form a rib pattern.

The PDP substrate was placed in an electric furnace,
To 570 ° C at a rate of 10 ° C / min.
By firing for 0 minutes, a PDP substrate was manufactured. The photosensitive resin composition on the PDP substrate was completely decomposed, and there was no discoloration of the ribs and no decrease in electric resistance.

Example 3 (i) Preparation of photosensitive resin composition for microfabrication The following components (1) 140 parts by weight of PVA aqueous solution of Example 1 (2) Polyvinyl acetate emulsion (MA-6, manufactured by Hoechst Gosei Co., Ltd.) (Solid content: 50%, average particle size: 6 μm) 150 parts by weight were mixed by a stirrer for 1 hour, followed by filtration through a 70 μm glass filter, and 100 parts by weight of the filtrate was added with 3-methoxy-4-diazo as a diazo compound as a diazo compound. Add 8 parts by weight of a 20% by weight aqueous solution of a condensate of diphenylamine sulfate and 4,4′-dimethoxydiphenyl ether in a phosphoric acid bath (condensation ratio 2: 1), stir and remove bubbles to remove photosensitive resin for fine processing. A composition was prepared.

(Ii) Formation of ribs Next, the following composition: 5 parts by weight of ethyl cellulose (manufactured by Hercules: TKK021) 320 parts by weight of sodium borosilicate glass powder (average particle diameter 12 μm) 320 parts by weight of ethylene glycol monoethyl ether acetate 75 parts by weight The resulting paste composition was kneaded well and applied to a PDP substrate so that the film thickness after drying was 150 μm, and dried at 150 ° C. for 20 minutes to form a rib forming layer. The rib-forming photosensitive resin composition adjusted as described above is applied on the rib forming layer such that the film thickness after drying is 30 μm.
It was dried and irradiated with an energy amount of 400 mJ / cm ² by an ultra-high pressure mercury lamp through a negative mask of 10 μm line / 120 μm space. Thereafter, spray development was performed for 90 seconds with warm water at 40 ° C., followed by washing with water.
After drying for 0 minutes, a rib definition mask pattern was obtained. The resulting rib definition mask pattern was visually observed. The pattern did not show any chipping or peeling, and no altered layer caused by seepage into the surface of the rib forming layer was observed.
Was formed satisfactorily.

Through the above-mentioned rib defining mask pattern,
The abrasive material of C # 800 was sandblasted at a blast pressure of 0.5 kg / cm ² for 5 minutes to cut the rib forming layer.
Next, after immersing in a 2% by weight sodium periodate solution for 120 seconds, the residue was sprayed with water at 22 ° C. to remove the remaining water-soluble resin composition layer. The cross-sectional shape of the rib pattern obtained on the PDP substrate was substantially rectangular.

The PDP substrate was placed in an electric furnace,
To 570 ° C at a rate of 10 ° C / min.
By firing for 0 minutes, a PDP substrate was manufactured. The photosensitive resin composition on the PDP substrate was completely decomposed, and there was no discoloration of the ribs and no decrease in electric resistance.

Example 4 The photosensitive resin composition used in Example 3 was applied on a PDP substrate so that the film thickness after drying was 100 μm,
At 30 ° C. for 30 minutes, and 1 J /
Exposure was performed with an energy amount of cm ² . Subsequently, it was spray-developed with warm water at 40 ° C. for 120 seconds, washed with water, and dried at 45 ° C. for 20 minutes to obtain a lift-off pattern.

Next, 0.5 parts by weight of hydroxypropyl cellulose (Nippon Soda Chemical Co., Ltd .: HPC) 9.5 parts by weight of hydroxypropyl methacrylate Polyoxyethylene monoacrylate AE-350 (manufactured by NOF Corporation) 7 parts by weight ・ Isgacure 651 (manufactured by Ciba-Geigy) 3 parts by weight ・ Sodium borosilicate glass powder 80 parts by weight A well kneaded paste composition is applied so that the space of the lift-off pattern is completely filled.
Exposure was performed with an energy amount of 1 J / cm ² , and the film was immersed in a 2% by weight sodium periodate solution for 120 seconds. Then 22
Spray with water at ℃, remove the remaining photosensitive resin composition,
A rib pattern was formed on a PDP substrate.

The PDP substrate was fired in the same manner as in Example 3 to produce a PDP substrate. The photosensitive resin composition was completely decomposed, and there was no discoloration of the ribs and no decrease in electric resistance.

Comparative Example 1 In Example 3, PVA (T-3 manufactured by Nippon Synthetic Chemical Co., Ltd.) was used.
50, carboxyl group-modified polyvinyl alcohol, Na
A rib was formed in the same manner as in Example 3 except that a 15% by weight aqueous solution having a content of 0.18% by weight) was used. Turned black, and a decrease in electric resistance was also confirmed.

[0033]

The photosensitive fat composition for fine processing of the present invention comprises:
It contains a polymer having an alkali content of 200 ppm or less as a binder component, and does not deteriorate the insulating properties of the insulating material in fine processing using the same. Especially PD
In the processing of P-ribs, there is no decrease in insulation properties,
There is no decrease in light emission luminance.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Toshimi Aoyama 150 Nakamurako, Nakahara-ku, Kawasaki-shi, Kanagawa Inside Tokyo Ohka Kogyo Co., Ltd.

Claims (4)

[Claims] 1. A photosensitive resin composition for fine processing comprising a polymer having an alkali content of 200 ppm or less as a main component. 2. A photosensitive resin composition for fine processing comprising a polymer having an alkali content of 200 ppm or less, a monomer having at least one ethylenically unsaturated group, and a photopolymerization initiator. 3. A photosensitive resin composition for fine processing, comprising a polymer having an alkali content of 200 ppm or less, a diazo compound and a polymer emulsion. 4. A rib forming layer is provided on a substrate, and the photosensitive resin composition for fine processing according to claim 3 is laminated thereon, and then actinic rays are irradiated through a mask pattern to form a rib defining mask pattern. Forming a rib pattern by sandblasting and baking.