JP3784222B2 - Stripping solution for photopolymerizable photosensitive material for rib pattern formation and rib pattern forming method using the same - Google Patents

Description

[0001]
[Industrial application fields]
The present invention relates to a method for forming a peeling liquid and ribs pattern using the same for the photopolymerizable light-sensitive material, more particularly a stripping solution of the rib pattern forming photopolymerizable light-sensitive material for use in the manufacture of plasma display panels and it The present invention relates to a rib pattern forming method used.
[0002]
[Prior art]
In the manufacture of a conventional plasma display panel (hereinafter referred to as PDP), there is a process of forming ribs for spacers between electrodes, cell partition walls, etc. As a method of forming this rib, an insulating paste composition is formed on a substrate. A rib forming layer made of a product is formed, a photosensitive layer pattern is provided thereon, the exposed rib forming layer is removed by sand blasting using the photosensitive layer pattern as a protective mask, and then the remaining photosensitive layer pattern is removed with a peeling solution. A method of removing, or forming a photosensitive layer pattern on a substrate, forming a rib forming layer made of an insulating paste composition, polishing and removing the rib forming layer on the photosensitive layer pattern, and then removing the photosensitive layer pattern with a peeling solution For example, a lift-off method for removing slag. As the photopolymerizable photosensitive material for forming the photosensitive layer pattern, an acrylic photosensitive material is generally used. For removing the photosensitive layer pattern, for example, see JP-A-1-158444 (a). A stripping solution comprising an alcohol solvent, (b) at least one selected from a halogen solvent, an ether solvent and an aromatic solvent and (c) a quaternary ammonium salt, and JP-A 61-20947 As seen in the publication, a stripping solution containing methylene chloride, alcohols, and 1,2-dichloroethane as essential components has been used. However, the stripping solution described in JP-A-1-158444 does not sufficiently dissolve and remove the photosensitive layer pattern, causing pattern loss and making it difficult to form a highly accurate rib pattern. Further, the stripping solution described in JP-A-61-20947 swells and strips the photosensitive layer pattern, so that the peeled photopolymerizable photosensitive material is reattached to the substrate and the rib layer, and a defective product remains as a residue. There were drawbacks that caused it to occur.
[0003]
[Problems to be solved by the invention]
In view of such a current situation, the present inventors have conducted extensive research, and as a result, have made photopolymerizable urethane (meth) acrylate compounds having at least two acryloyl groups or methacryloyl groups, alkali-soluble polymer compounds, and initiation of photopolymerization. The photosensitive layer pattern can be dissolved and removed satisfactorily by using a solution containing an organic amine, quaternary ammonium salt and water as a stripping solution for the photopolymerizable photosensitive material for rib pattern formation containing an agent, and a highly accurate rib pattern The present invention has been completed by finding that it can be easily formed. That is,
[0004]
The present invention relates to a plasma display panel comprising a photopolymerizable urethane (meth) acrylate compound having at least two acryloyl groups or methacryloyl groups, an alkali-soluble polymer compound, and a photopolymerization initiator, which are used for producing a PDP . An object of the present invention is to provide a stripping solution that can satisfactorily dissolve and remove the photopolymerizable photosensitive material for rib pattern formation .
[0005]
Another object of the present invention is to provide a method for forming a highly accurate rib pattern using the above stripping solution.
[0006]
[Means for Solving the Problems]
The present invention that achieves the above object is a rib pattern forming light comprising a photopolymerizable urethane (meth) acrylate compound having at least two acryloyl groups or methacryloyl groups, an alkali-soluble polymer compound, and a photopolymerization initiator. A photopolymerizable photosensitive resin for rib pattern formation , which is a stripping solution for a polymerizable photosensitive material, and the stripping solution contains (a) an organic amine, (b) a quaternary ammonium salt, and (c) water. according to wood charge stripping solution and method of forming a rib pattern using the same.
[0007]
Hereinafter, the present invention will be described in detail.
The (a) organic amine of the photopolymerizable photosensitive material stripping solution for forming a rib pattern in the present invention has the general formula 2
[0008]
[Chemical 2]
^(Wherein, R 1, ^{R 2} identical or different substituents, hydrogen atom, Al kill group having 1 to 4 carbon atoms, an alkanol group having 2 to 6 carbon atoms, an alkoxy group, ^{R 3} is water group Represents an amino group, a cycloalkyl group, or a phenyl group, n represents an integer of 1 to 6, and R ³ may further have a substituent.)
Specifically, monoethanolamine, diethanolamine, diisopropylamine, N-methylethanolamine, N-methyldiethanolamine, 3-amino-1-propanol, 4-amino-1-butanol, cyclohexylamine are used. , Diallylamine, N-methylbenzylamine, N, N-dimethylbenzylamine, N-alkylmorpholine, 1,2 diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, diethylenetriamine, triethylenetetramine, etc. be able to. Monoethanolamine is particularly preferable. The organic amines may be used alone or in combination of two or more.
[0009]
Specific examples of the quaternary ammonium salt (b) of the present invention include tetramethylammonium hydroxide, choline, tetrahydroxyethylammonium hydroxide, monomethyltrihydroxyethylammonium hydroxide, and particularly tetra. Methyl ammonium hydroxide and choline are preferred. The quaternary ammonium salts may be used alone or in combination of two or more.
[0010]
Although the rib pattern forming photopolymerizable photosensitive materials stripping solution of the present invention is prepared by the the components (a) and (b) were dissolved in water. The mixing ratio of component (a) 0.5 to 15 weight %, Component (b) 0.5 to 15% by weight and water 70 to 90% by weight are selected.
[0011]
As the insulating paste for forming the rib forming layer, a paste composition made of an insulating material, an organic binder, and an organic solvent is used. As the insulating material, an inorganic substance such as Al ₂ O ₃ , PbO, B ₂ O ₃ , SiO ₂ , ZnO, MgO, SnO ₂ is used. Preferably, a low melting glass powder that becomes a binder during firing is used. It may be included. Examples of the low melting point glass powder include glasses having a softening point of about 350 to 600 ° C. such as low melting point lead glass and low melting point zinc glass.
[0012]
Further, a photopolymerizable sensation for rib pattern formation comprising a photopolymerizable urethane (meth) acrylate compound having at least two acryloyl groups or methacryloyl groups forming the photosensitive layer , an alkali-soluble polymer compound and a photopolymerization initiator . The optical material is a material that has sandblast resistance and can be easily peeled and removed . For example, a photopolymerizable urethane (meta) having at least two acryloyl groups or methacryloyl groups described in JP-A-9-127692 is disclosed. ) A photopolymerizable photosensitive material containing an acrylate compound, an alkali-soluble polymer compound and a photopolymerization initiator . The photopolymerizable urethane (meth) acrylate compound having at least two acryloyl groups or methacryloyl groups includes a compound having a terminal isocyanate group (—NCO group) obtained by reacting a diol compound and a diisocyanate compound, and a hydroxyl group. The reaction product with the (meth) acrylate compound which has this is mentioned, The urethane acrylate which has at least 3 or more urethane bond in a molecule | numerator is especially suitable. Examples of the alkali-soluble polymer compound include acrylic acid resin, methacrylic acid resin, acrylic acid or methacrylic acid copolymer, carboxymethyl cellulose, cellulose acetate phthalate, and the like, and a copolymer component of the acrylic acid or methacrylic acid copolymer. As fumaric acid, maleic acid, crotonic acid, cinnamic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, fumaric acid Monomethyl, monoethyl fumarate, monopropyl fumarate, monomethyl maleate, monoethyl maleate, monopropyl maleate, sorbic acid and the like, and as partial acetate of cellulose, dicarboxylic acid or tricarboxylic acid, Example, if succinic acid, adipic acid, cellulose compound obtained by reacting trimellitic acid are preferred.
[0013]
Specific examples of the photopolymerization initiator include benzophenone derivatives such as benzophenone, 4,4′-bis (dimethylamino) benzophenone, 3,3-dimethyl-4-methoxy-benzophenone, anthraquinone, 2-methylanthraquinone, 2- Anthraquinone derivatives such as ethyl anthraquinone, tert-butylanthraquinone, 1-chloroanthraquinone, benzoin alkyl ether derivatives such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, 2-methyl- Acetophenone derivatives such as-[4- (methylthio) phenyl] -2-morpholino-1-propanone, thioxanthone derivatives such as 2-chlorothioxanthone, diethylthioxanthone, isopropylthioxanthone, diisopropylthioxanthone, benzyl, 2,4,6- (trihalo) Methyl) -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, dimethylbenzyl ketal, trimethylbenzoyldiphenylphosphine oxide, tribromomethylphenylsulfone, 2-benzyl-2-dimethylamino-1- (4-morpholine Nophenyl) -butan-1-one and the like. These photopolymerization initiators can be used alone or in combination of two or more.
[0014]
The proportion of the photopolymerizable photosensitive material for forming the rib pattern is 50 to 90% by weight of the photopolymerizable urethane (meth) acrylate compound having at least two acryloyl groups or methacryloyl groups, and 5 of the alkali-soluble resin cellulose. The amount of the photopolymerization initiator is preferably in the range of 0.1 to 20% by weight with respect to the total amount of urethane acrylate and alkali-soluble resin cellulose.
[0015]
As a rib pattern forming method using the stripping solution of the photopolymerizable photosensitive material for rib pattern formation of the present invention, (i) a rib forming paste is applied on a substrate such as glass and dried to form a rib forming layer. And a photopolymerizable photosensitive material for rib pattern formation comprising a photopolymerizable urethane (meth) acrylate compound having at least two acryloyl groups or methacryloyl groups thereon , an alkali-soluble polymer compound and a photopolymerization initiator. Apply and dry, or use a dry film with the photopolymerizable photosensitive material disposed between the flexible support film and the release film, peel the release film and press-fit on the rib-forming layer To form a photopolymerizable photosensitive layer, and after drying, attach a mask with a predetermined mask pattern, irradiate actinic light from above the mask pattern, and develop Create a photosensitive layer pattern, then the rib forming layer exposed the photosensitive layer pattern as a protective pattern by sandblasting with sand blasting material is ground and removed, the rib pattern forming photopolymerizable photosensitive of the present invention the photosensitive layer pattern remaining removed material stripping solution, the photopolymerizable urethane (meth) acrylate compound having at least two acryloyl or methacryloyl groups in the firing method and (ii) on the substrate, alkali-soluble polymeric compound and a photopolymerization initiator A photosensitive layer is formed using a photopolymerizable photosensitive material for rib pattern formation containing, and actinic rays are irradiated through a mask pattern, developed to create a photosensitive layer pattern, and a rib forming paste is applied on the entire surface of the substrate. After applying to and drying to form a rib-forming layer, the rib-forming layer on the photosensitive layer pattern is polished and removed. In removing the photosensitive layer pattern on the substrate by using a rib pattern forming photopolymerizable photosensitive material stripping solution of the present invention include a method of baking (liftoff method). Examples of the peeling treatment include dipping, showering, spraying, and the like, and a dipping method is preferable. This peeling treatment is performed at a temperature of 15 to 60 ° C. for 1 to 10 minutes. Examples of the sandblasting material used in the sandblasting treatment include fine particles of about 1 to 500 μm such as glass beads, SiC, SiO ₂ , Al ₂ O ₃ , ZrO ₂ , and organic plastic materials.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
EXAMPLES Next, although this invention is demonstrated further in detail based on an Example, this invention is not limited at all by these examples.
[0017]
【Example】
Example 1
White low melting point glass frit containing PbO 100 parts by weight, ethyl cellulose 2 parts by weight, dibutyl phthalate (plasticizer) 5 parts by weight, α-terpineol 20 parts by weight and Oil Yellow 105 (azo dye, manufactured by Orient Chemical Industries) 5 A rib-forming paste obtained by kneading and mixing parts by weight with three rolls was applied onto soda glass by a screen printing method so that the film thickness after drying was 150 μm, and dried to obtain a rib-forming layer. . Next, Audil BF-703 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), which is a dry film of a photopolymerizable material for rib pattern formation , is placed on the rib forming layer with a substrate temperature of 80 ° C., a lamination temperature of 105 ° C., and a lamination pressure of 2.5 kg / cm ^Then , a photosensitive dry film resist layer was formed by laminating at ² and exposed at an intensity of 200 mJ / cm ² with a 3.5 W ultrahigh pressure mercury lamp through a test mask. After exposure, spray development was performed with a 0.2 wt% aqueous sodium carbonate solution to obtain a photosensitive layer pattern.
[0018]
Next, using the photosensitive layer pattern as a mask, sandblasting was performed with an abrasive of glass beads # 800 (manufactured by Toshiba Parrotini Co., Ltd.), and the exposed rib-forming layer was removed by cutting. Then, 1% by weight of monoethanolamine, tetramethylammonium hydroxy The remaining photosensitive layer pattern was peeled and removed by dipping in a 40 ° C. aqueous solution of a stripping solution comprising 1% by weight of water and 98% by weight of water. The time required for peeling was 25 seconds. There was no residual photosensitive layer pattern, and defects in the rib pattern were not confirmed.
[0019]
Comparative Example 1
A photosensitive layer pattern was formed in the same manner as in Example 1, and the remaining photosensitive layer pattern was peeled and removed by dipping in a 40 ° C. solution of a stripping solution composed of a 1 wt% monoethanolamine aqueous solution. The time required for the remaining photosensitive layer pattern was 40 seconds, and a resist residue was partially confirmed.
[0020]
Comparative Example 2
A photosensitive layer pattern was formed in the same manner as in Example 1, and the remaining photosensitive layer pattern was peeled and removed by dipping in a 40 ° C. solution of a stripping solution composed of a 1% by weight tetramethylammonium hydroxide aqueous solution. The time required for the remaining photosensitive layer pattern was 40 seconds, and a resist residue was partially confirmed. Moreover, the defect of the rib pattern was also confirmed.
[0021]
【The invention's effect】
The photopolymerizable photosensitive material stripping solution for rib pattern formation of the present invention dissolves and removes the photopolymerizable photosensitive material for rib pattern formation having sandblast resistance, and there is no residue of the photosensitive layer pattern and a highly accurate rib pattern can be obtained. Easy to manufacture.

Claims (4)

A photopolymerizable photosensitive material for rib pattern formation of a plasma display panel, comprising a photopolymerizable urethane (meth) acrylate compound having at least two acryloyl groups or methacryloyl groups, an alkali-soluble polymer compound and a photopolymerization initiator. A stripping solution, wherein the stripping solution is (a) an organic amine represented by the general formula 1
(Wherein R ¹ and R ² are the same or different substituents and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkanol group having 2 to 6 carbon atoms, or an alkoxy group, and R ³ represents a hydroxyl group or an amino group. , A cycloalkyl group and a phenyl group, n represents an integer of 1 to 6, and R ³ may further have a substituent.) , (B) tetramethylammonium hydroxide, choline, tetrahydroxyethylammonium A photopolymerizable photosensitive material stripping solution for forming a rib pattern, comprising at least one quaternary ammonium salt selected from a hydroxide, a monomethyltrihydroxyethylammonium hydroxide group, and (c) water. (A) The organic amine is monoethanolamine, diethanolamine, diisopropylamine, cyclohexylamine, diallylamine, N-methylbenzylamine, N, N-dimethylbenzylamine, N-alkylmorpholine, N-methylethanolamine, N-methyldiethanolamine The photopolymerizable photosensitive material stripping solution for forming a rib pattern according to claim 1, wherein (B) The photopolymerizable photosensitive material stripping solution for forming a rib pattern according to claim 1, wherein the quaternary ammonium salt is selected from tetramethylammonium hydroxide and choline. A rib pattern forming light comprising a photopolymerizable urethane (meth) acrylate compound having at least two acryloyl groups or methacryloyl groups in a rib forming layer formed on a substrate, an alkali-soluble polymer compound, and a photopolymerization initiator. A polymerizable photosensitive material layer is provided, irradiated with actinic rays through a mask film, subjected to a development process, a portion not irradiated with actinic rays is removed to form a photosensitive layer pattern, and the photosensitive layer pattern is exposed as a mask. 2. A rib pattern forming method comprising: removing a rib forming layer by sandblasting and then removing the photosensitive layer pattern with the photopolymerizable photosensitive material stripping solution for forming a rib pattern according to claim 1.