JP2006349718A - Photopolymerizable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photopolymerizable composition excellent also in adhesion to a substrate and capable of forming an elaborate fine pattern with very little residue on baking. <P>SOLUTION: The photopolymerizable composition contains at least a polymeric binder, a photopolymerizable monomer and a photopolymerization initiator. The polymeric binder is a polymeric binder containing at least a cellulose derivative and the photopolymerizable monomer contains at least one selected from the acrylic compounds represented by formula 1, wherein R1 and R2 each denote H, hydroxyl or a 1-9C alkyl which may have hydroxyl; and m and n each denote an integer, provided that the sum of m and n is ≤14. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photopolymerizable composition that can be applied to fine pattern formation processing such as flat display panel substrates and the formation of small electronic components, and in particular has excellent adhesion to the substrate, high burn-off property, and is dense and good. The present invention relates to a photopolymerizable composition capable of forming a fine pattern having various shapes.

  Conventionally, photopolymerizable compositions have been widely used in resists for plate making, resists for fine processing, varnishes for photosensitive coatings, glass adhesives, and the like. Such a photopolymerizable composition is generally formed from a composition containing a polymer binder, a photopolymerizable monomer, and a photopolymerization initiator. Among them, a photopolymerizable composition in which the photopolymerizable monomer is an acrylic compound such as acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, pentaerythritol triacrylate, and pentaerythritol trimethacrylate. It is used as a resist for microfabrication in electronic component manufacturing.

  The microfabrication using a photopolymerizable composition containing such an acrylic photopolymerizable monomer is a so-called pattern processing through a mask after forming a photopolymerizable composition film on a substrate. Lithographic processing is common. In recent years, this fine processing technology has further advanced, and finer processing has been demanded. Along with that, characteristics required for photopolymerizable compositions used for microfabrication are not only sensitivity and resolution, but also adhesion to the substrate, and baking to remove photosensitive components that are no longer needed after processing the substrate. The burn-off property and the denseness of the film after firing have been required.

  A conventional photopolymerizable composition containing a polymer binder, an acrylic compound, and a photopolymerization initiator is excellent in sensitivity, resolution, and the like. However, since the adhesiveness to the substrate and the burn-off property are insufficient, there are many firing residues, and a porous fired film having a high porosity after firing is obtained. For this reason, there is a problem in that various defects due to the firing residue and the porous fired film occur. Accordingly, there is an eager desire to provide an excellent photopolymerizable composition that can produce a dense fired film with very little fired residue.

Moreover, using a photopolymerizable composition containing a photopolymerizable monomer composed of a specific acrylic compound is disclosed as a technique for improving such problems (for example, Patent Document 1). .
Japanese Patent No. 3329777

  However, according to the photopolymerizable composition using a photopolymerizable monomer composed of a specific acrylic compound, it is said that the sensitivity and resolution are excellent, and the adhesion to the substrate and the burn-out property are improved. However, when it is applied to a flat display panel that requires ultra-fine processing in recent years, there are the following problems.

  That is, when a minimum line width of 30 μm or less is required as in a high-definition display panel, the adhesiveness with the substrate is insufficient, and a baked residue remains after baking, resulting in a porosity. There is a problem that a high-quality porous fired film is produced, and quality defects occur in fine processing of flat display panels and the like.

  The present invention has been made in view of such problems, and is excellent in sensitivity, resolution, and adhesion to a substrate, has very few firing residues, and is used for microfabrication capable of obtaining a dense fired film. An object is to provide a photopolymerizable composition.

  In order to solve the above problems, the photopolymerizable composition of the present invention is a photopolymerizable composition containing at least a polymer binder, a photopolymerizable monomer, and a photopolymerization initiator, and comprises a polymer binder. Is a polymer binder containing at least a cellulose derivative, and the photopolymerizable monomer contains at least one selected from acrylic compounds represented by the general formula 1.

  However, R1 and R2 in a formula are a C1-C9 alkyl group which may have a hydrogen atom, a hydroxyl group, and a hydroxyl group, and m and n are integers whose sum of m and n is 14 or less.

  According to such a photopolymerizable composition, in fine processing, sensitivity and resolution are excellent and adhesion to a substrate is excellent, and a fine and good pattern having a minimum line width of 30 μm or less can be formed. A dense fired film can be obtained with very little fired residue resulting from the polymerizable monomer.

  Further, the photopolymerizable monomer is preferably an acrylic compound in which m and n in the general formula 1 are each 0, and the photopolymerizable monomer is not water-soluble. Peeling is suppressed and adhesion with the substrate is improved.

  Further, it may be a photopolymerizable composition containing at least one of a conductive inorganic material, an insulating inorganic material, and an inorganic pigment material, and thereby a conductor circuit pattern, a partition pattern, a dielectric pattern in a flat display panel, etc. A body pattern, a phosphor pattern, etc., or minute conductors, resistors, dielectrics, etc. in electronic parts can be formed with high accuracy and high quality.

  Furthermore, it may be a photopolymerizable composition formed on a flexible film to form a photosensitive film, which improves productivity when forming a pattern on a flat display panel substrate, The film thickness accuracy can be improved.

  As described above, according to the photopolymerizable composition of the present invention, it is possible to form a good pattern with a minimum line width of 30 μm or less after development with excellent sensitivity and resolution and excellent adhesion to the substrate, A dense fired film with little fired residue resulting from the photopolymerizable monomer can be obtained.

  Hereinafter, embodiments of the photopolymerizable composition of the present invention will be described.

(Embodiment)
The photopolymerizable composition in the embodiment of the present invention is a photopolymerizable composition containing a polymer binder as the A component, a photopolymerizable monomer as the B component, and a photopolymerization initiator as the C component.

  Specific examples of the polymer binder as component A include cellulose derivatives selected from hydroxypropylcellulose, ethylhydroxyethylcellulose, hydroxypropylmethylcellulose phthalate, and hydroxypropylmethylcellulose acetate. The above cellulose derivatives may be used alone or in combination of two or more. Also, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, monomethyl fumarate, monoethyl fumarate, fumaric acid Monopropyl, monomethyl maleate, monoethyl maleate, monopropyl maleate, sorbic acid, hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, hydroquinone monoacrylate, hydroquinone monomethacrylate, hydroquinone Diacrylate, hydroquinone di-2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypro Methacrylate, N-butyl acrylate, N-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxy acrylate, phenoxy methacrylate, isobornyl acrylate, isobornyl methacrylate , Ethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolethane tria Relate, trimethylolethane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, Cardoepoxy diacrylate, glycidyl methacrylate, ethylene glycol diacrylate, (meth) acrylate of these exemplified compounds were replaced with fumarate ester instead of fumarate, maleate ester instead of maleate, crotonic acid ester replaced with crotonate, itaconate Itaconic acid ester, urethane methacrylate, styrene, acrylamide, methacrylamide, acryloni Polymers or copolymers such as tolyl and methacrylonitrile can be contained in the component A. The above polymers or copolymers may be used alone or in combination of two or more.

  In the above, the content of the polymer binder of the component A can be contained in the range of 1 to 60 parts by weight in 100 parts by weight of the total of the components A, B and C.

  The photopolymerizable monomer as component B is at least one selected from the novel acrylic compounds represented by general formula 1 synthesized using malon as a starting material. By containing the body, the adhesion of the pattern formed with the photopolymerizable composition of the embodiment of the present invention to the substrate is improved, and a dense fired film is obtained with a very small amount of fired residue. Can be performed well.

  In addition, as the photopolymerizable monomer of the B component, particularly when an acrylic compound in which m and n in the general formula 1 are 0 is used, the photopolymerizable monomer itself is not water-soluble. Peeling is suppressed and adhesion is further improved.

  Specific examples of the acrylic compound represented by the general formula 1 include the compounds of (Chemical Formula 2) to (Chemical Formula 4), and more preferably, the acrylic compounds of (Chemical Formula 2) and (Chemical Formula 3). It is.

  Moreover, also in the above, content of the photopolymerizable monomer of B component can be contained in 1-60 weight part in 100 weight part of total of A component, B component, and C component. If the component B is less than 1 part by weight, photopolymerization cannot be expected, and if it exceeds the range, the burn-out property is deteriorated and a dense fired film cannot be obtained.

  In addition to the photopolymerizable monomer represented by the general formula 1 of component B described above, the photopolymerizable composition of the present invention is a known photopolymerizable monomer in order to improve coating film properties. In the range not impairing the purpose. Examples of the photopolymerizable monomer for improving the coating film characteristics include ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate, and trimethylol. Propane trimethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetra Acrylate, dipentaerythritol Tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, glycerol acrylate, glycerol methacrylate, cardoepoxy diacrylate, and (meth) acrylates of these exemplary compounds to fumarate Examples thereof include fumarate ester substituted, itaconic acid ester substituted for itaconate, and maleic acid ester substituted for maleate.

  Moreover, in the above, content of the photopolymerizable monomer which improves a coating-film characteristic can be contained in the range of 0-30 weight part in 100 weight part of total of A component, B component, and C component. .

  Furthermore, as the photopolymerization initiator of component C, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- ( 2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl- 6- (2-Bromo-4-methoxy) styrylphenyl-s-triazine, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (py-1-yl) phenyl] titanium, bis (cyclo Pentadienyl) -bis [2,6-difluoro-2- (py-1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis (2,3,4,5,6-pen Fluorophenyl) titanium, bis (cyclopentadienyl) -bis [2,5-difluoro-3- (pyr-1-yl) phenyl] titanium, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2 -Diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl] 2-hydroxy-2-methyl-1-propan-1-one, 2,4-diethylthioxanthone, 2,4-dimethylthio Xanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-benzoyl-4′-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4 -Ethyl dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 2-dimethylhexyl 4-dimethylaminobenzoate, 2-isoamyl 4-dimethylaminobenzoate, 2,2-diethoxyacetophenone, benzyldimethyl ketal, benzyl -Β-Methoxyethyl acetal 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, bis (4-dimethylaminophenyl) ketone, 4,4′-bisdiethylaminobenzophenone, benzyl, benzoin , Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methyl Thioxanthone, 2-isopropylthioxanthone, dibenzosuberone, α, α-dichloro-4-phenoxyacetophenone, pentyl-4-dimethylaminobenzoate 2-(o-chlorophenyl) such -4,5-diphenyl imidazolylmethyl dimer and the like. C component can be used individually or in combination of 2 or more types.

  Moreover, in the above, content of the photoinitiator of C component can be contained in 0.01-20 weight part in 100 weight part of total of A component, B component, and C component.

  Furthermore, the photopolymerizable composition of the embodiment of the present invention can contain at least one of a conductive inorganic material, an insulating inorganic material, and an inorganic pigment material as the D component. Examples of the D component inorganic material include a conductive inorganic material as the D1 component, an insulating inorganic material as the D2 component, and an inorganic pigment material as the D3 component, and each component of D1, D2 and D3 can be mixed according to the application. Can be designed and mixed as appropriate.

  In the above, for example, the conductive inorganic material of the D1 component is a metal material containing at least one selected from the group consisting of Au, Ag, Cu, Pd, Pt, Al, and Ni, and each can be used alone or as a mixed powder. . As a result, for example, bus electrodes and address electrodes on the front plate and the back plate of the plasma display panel can be formed as wiring electrodes or conductor circuit patterns that are narrow but dense and have low electrical resistance.

In the above, as the D2 component insulating inorganic material, glass, ceramics (cordylite, etc.) can be used. Specifically, PbO—SiO ₂ system, PbO—B ₂ O ₃ —SiO ₂ system, ZnO—SiO ₂ system, ZnO—B ₂ O ₂ —SiO ₂ system, BiO—SiO ₂ system, BiO—B ₂ O _2. -SiO ₂ system borosilicate lead glass, borosilicate zinc glass, or glass powder such as borosilicate bismuth glass, cobalt oxide, iron oxide, chromium oxide, nickel oxide, copper oxide, manganese oxide, neodymium oxide, vanadium oxide, Cerium tipe yellow, cadmium oxide, ruthenium oxide, silica, magnesia, spinel, Na, K, Mg, Ca, Ba, Ti, Zr, Al, and other oxides, ZnO: Zn, Zn ₃ (PO ₄ ) _{2 : Mn, 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 A1 5 O 12: Eu, YBO 3: Eu, (Y, Gd) BO 3: Eu, GdBO 3: Eu, ScBO 3: Eu, LuBO 3: Eu, Zn 2 SiO 3 _{: Mn, BaAl 12 O 19:} Mn, SrAl 13 O 19: Mn, CaAl 13 O 19: Mn, YBO 3: Tb, BaMgAl 14 O 23: Mn, LuBO 3: Tb, GdBO: Tb, ScBO 3: Tb, Sr ₆ Si ₃ O ₃ C ₁₄ : Eu, ZnS: (Cu, Al), ZnS: Ag, Y ₂ O ₂ S: Eu, ZnS: Zn, (Y, Cd) BO ₃ : Eu, BaMgAl ₁₂ O ₂₃ : Phosphor powder such as Eu, etc., which can be used alone or as a mixed powder. Thereby, for example, the dielectric layer on the front plate of the plasma display panel, the dielectric layer on the back plate, the partition, the phosphor layer, and the like can be formed in a fine and dense pattern.

  Moreover, in the above, as an inorganic pigment material of D3 component, the inorganic pigment material which consists of an oxide of the metal containing at least 1 sort (s) chosen from Fe, Co, Cu, Cr, Mn, and Al group can be used. Thereby, for example, in the front plate of a plasma display panel, it can be used for blackening a black matrix or a bus electrode having a narrow width and a low electric resistance.

  By preparing a photopolymerizable composition containing an inorganic material containing at least one of a conductive inorganic material, an insulating inorganic material and an inorganic pigment material, a printing paste containing these is prepared and applied, and then After exposure and development, baking is performed. As a result, conductor circuit patterns, partition patterns, dielectric patterns, phosphor patterns, etc. in plasma display panels, FEDs, SEDs, etc., which are flat display panels, can be formed as a dense fired film with a small minimum line width. it can. In addition, minute conductors, resistors, dielectrics, and the like in electronic components can be formed as a dense fired film with a small minimum line width.

  Moreover, in the above, content of the inorganic material of D component can contain in 1-80 weight part in 100 weight part of total of A component, B component, C component, and D component.

  In addition, the photopolymerizable composition of the embodiment of the present invention is used by dispersing the A component, the B component, the C component, and the D component in water or dissolving them in an organic solvent as the E component. Specific examples of the organic solvent for component E include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate 3-ethyl-3-methoxybutyl acetate, - ethoxy butyl acetate, 4-ethoxy butyl acetate, 4-propoxybutyl acetate, 2-methoxy-pentyl acetate. The organic solvent for the component E can be used alone or in combination of two or more.

  In addition, the photopolymerizable composition of the embodiment of the present invention includes additives such as a photosensitizer, a filler, a diluent, an antifoaming agent, a leveling agent, a thickener, and a stabilizer as necessary. Can be added.

  In addition, when precise processing such as manufacture of electronic parts is required, a photosensitive film formed by applying and drying the photopolymerizable composition of the embodiment of the present invention on a flexible film, for example. It is good to use. The photosensitive film is, for example, a photopolymerizable composition dissolved in a solvent or dispersed in water in a flexible film made of a synthetic resin film such as polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, polyvinyl chloride having a film thickness of 15 to 125 μm. Is applied by using an applicator, a bar coater, a wire bar coater, a roll coater, a curtain flow coater or the like so as to have a dry film thickness of 2 to 100 μm and dried. In addition, if necessary, a release film may be attached to stably protect the photosensitive layer when not in use. As this release film, a polyethylene terephthalate film, a polypropylene film, a polyethylene film, or the like having a thickness of about 15 to 125 μm coated or baked with silicone is suitable.

  As described above, the photopolymerizable composition is applied onto a flexible film and dried to form a film to form a photosensitive film, thereby improving productivity when forming a pattern on a flat display panel substrate. Further, the film thickness accuracy can be improved.

  Next, a method for forming a pattern using the photopolymerizable composition of the embodiment of the present invention will be described.

  First, the photopolymerizable composition of the embodiment of the present invention is dissolved in an organic solvent to prepare a coating paste, which is coated on a glass substrate or the like and dried to form a coating film of the photopolymerizable composition. The coating film is irradiated with an actinic ray such as an ultraviolet ray, an excimer laser, an X-ray, and an electron beam through a mask having a predetermined pattern to perform image exposure. Next, development is performed using a general-purpose alkali developer or water, and the unirradiated part or irradiated part is dissolved and removed to form a fine pattern of the photopolymerizable coating film on the glass substrate. Examples of the alkaline component of the alkaline developer used for development include first alkali metal hydroxides such as Li, Na, and K, carbonates, bicarbonates, phosphates, pyrophosphates, benzylamine, butylamine, and the like. Secondary amines such as tertiary amine, dimethylamine, dibenzylamine and diethanolamine, tertiary amines such as trimethylamine, triethylamine and triethanolamine, cyclic amines such as morphophore, piperazine and pyridine, polyamines such as ethylenediamine and hexamethylenediamine Tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylbenzylammonium hydroxide, and other ammonium hydroxides, trimethylsulfonate Muhidorokishido such, diethyl methyl sulfonium hydroxide, sulfonium hydroxide such as dimethyl benzyl sulfonium hydroxide, choline, and the like silicate-containing buffers.

  Next, the patterned photopolymerizable coating film containing a polymer binder or an inorganic material is baked at a temperature in the range of 350 to 750 ° C. to form a fired product having a fine pattern on the substrate.

  That is, the above-described method for forming a fine pattern includes a step of applying a coating paste containing a photopolymerizable composition on a substrate and drying, an exposure step of selectively irradiating actinic rays, and unnecessary areas. It has a developing step for removing and forming a fine pattern, and a baking step for baking and solidifying at a temperature in the range of 350 to 750 ° C.

  When a pattern is formed by the above-described method using the photopolymerizable composition of the embodiment of the present invention, it has excellent sensitivity to actinic rays and good resolution, and even when the minimum line width after development is 30 μm or less, It was possible to form a dense fired film having excellent adhesiveness and extremely little fired residue resulting from the photopolymerizable monomer after firing.

  Therefore, by using the photopolymerizable composition according to the embodiment of the present invention as a material for forming a component on the flat display panel substrate, it is possible to realize a flat display panel having high definition, excellent reliability and quality. it can. In addition, the photopolymerizable composition of the embodiment of the present invention can be applied to the formation of a conductor, a resistor, and a dielectric for electronic parts, and a high-performance electronic part can be realized.

  Hereinafter, specific examples of the paste for forming the conductive bus electrode formed on the front plate of the plasma display panel using the photopolymerizable composition of the present invention and comparative examples for them will be described. To do. In the following examples and comparative examples, the concentration of each material is shown in parts by weight.

Example 1
In this example, the following components A to E were used, and after stirring with a stirrer, the mixture was kneaded with a three-roll mill to prepare a photopolymerizable composition paste.

Component A: hydroxypropyl cellulose 4.5 parts by weight Component B: acrylic compound represented by (Chemical Formula 2) 4.5 parts by weight Component C: 2-methyl-1- [4- (methylthio) phenyl] -2-morpho Linopropan-1-one
0.5 parts by weight
2,4-diethylthioxanthone 0.5 parts by weight D component: 73 parts by weight of silver powder as a conductive inorganic material
Glass powder as insulating inorganic material 2 parts by weight E component: 3-methyl-3-methoxybutyl acetate 15 parts by weight (Example 2)
As the photopolymerizable monomer of component B used in Example 1, photopolymerizability was carried out in the same manner as in Example 1, except that an acrylic compound represented by (Chemical Formula 3) was used instead of (Chemical Formula 2). A composition was prepared.

(Example 3)
Photopolymerizable by the same operation as in Example 1 except that an acrylic compound represented by (Chemical Formula 4) was used instead of (Chemical Formula 2) as the photopolymerizable monomer of Component B used in Example 1. A composition was prepared.

(Comparative Example 1)
A photopolymerizable composition was prepared in the same manner as in Example 1 except that pentaerythritol triacrylate was used in place of (Chemical Formula 2) as the photopolymerizable monomer of Component B used in Example 1.

(Comparative Example 2)
The same operation as in Example 1 except that the acrylic compound represented by (Chemical Formula 5), which is a conventional technique, was used in place of (Chemical Formula 2) as the photopolymerizable monomer of Component B used in Example 1. Thus, a photopolymerizable composition was prepared.

The above-mentioned photopolymerizable composition prepared in Examples 1 to 3 and Comparative Examples 1 and 2 was pasted on a glass substrate as a plasma display panel substrate using a 380 mesh screen. After drying for 30 minutes in a hot air drying oven at 0 ° C., the coating was applied to a thickness of 10 μm. Then, ultraviolet exposure was performed with an irradiation amount of 200 mJ / cm ² with an ultrahigh pressure mercury lamp through a pattern mask. Subsequently, spray development was performed for 30 seconds at a spraying pressure of ² kg / cm ² using water having a liquid temperature of 25 ° C. to form a bus electrode pattern. Thereafter, the bus electrode was heated in a baking furnace at a heating rate of 10 ° C./min and held at 590 ° C. for 10 minutes to form a finely patterned bus electrode, and the following characteristic items were evaluated.

  For adhesion, a negative mask having a line / space = 1/2 and a line width of 10 to 200 μm was used, and the reproducibility, shape, and disconnection of the line width after development and after baking were observed with an optical microscope. Evaluate based on the standard and read the minimum line width that is ○. In particular, the minimum line width that does not cause disconnection in the development process is used.

  ○ is a state in which all are good, and × is a state in which a dimensional deviation from a mask of ± 10 μm or more occurs in the line width reproducibility or there is a disconnection.

  The firing line shape was observed with an optical microscope after firing and evaluated according to the following criteria.

  ○ is a state in which the shape before firing is maintained, and × is a state in which the shape before firing is not maintained, and the line is broken or twisted.

  The density of the fired film was evaluated based on the following criteria by observing the surface and cross section of the fired pattern film with a scanning electron microscope after firing.

  ○ is a good and dense film, and x is a porous film with many voids in the film.

  As the evaluation of the bus electrode alone, the above-mentioned adhesion, fired line shape, and fired film density were evaluated. Furthermore, the dielectric paste is applied by screen printing on the bus electrode that has been patterned and fired so as to have a film thickness of 30 μm after drying, and is heated at a heating rate of 10 ° C./min in a firing furnace. A dielectric film was formed by baking at 590 ° C. for 10 minutes, and the following items were evaluated.

  The dielectric film defects were evaluated according to the following criteria by observing the formed dielectric film with an optical microscope.

  ○ indicates that there is no difference in the dielectric film defect between the portion with the bus electrode and the portion without the bus electrode, and × indicates a bubble or film protrusion compared with the portion with the bus electrode without the bus electrode. It shows a state with film defects such as.

  The evaluation results for these characteristic items are shown in Table 1.

  As shown in Table 1, in Examples 1 to 3, when the bus electrode was formed on the plasma display substrate using the photopolymerizable composition of the present invention, there was no peeling of the pattern after development. Thus, it was found that a fine pattern having a minimum line width of 30 μm or less can be formed after development and baking after excellent adhesion to the substrate. In particular, in Example 1, a minimum line width of 10 μm can be realized. In addition, as a result of component analysis of the fired bus electrode, it was confirmed that there were very few firing residues resulting from the photopolymerizable monomer. Further, from the line shape of the bus electrode and the observation of the surface and cross section, it was found that the film was denser and without voids than the comparative example. It was also found that film defects such as a dielectric layer formed on the bus electrode can be reduced as compared with the comparative example.

  When the photopolymerizable composition according to the present invention is used, it is possible to form a fine pattern with a fine film quality, which is useful in the fields of microelectronic parts, flat displays such as plasma displays, and the like.

Claims (4)

A photopolymerizable composition containing at least a polymer binder, a photopolymerizable monomer, and a photopolymerization initiator, wherein the polymer binder is a polymer binder containing at least a cellulose derivative, and the photopolymerizable monomer. The photopolymerizable composition, wherein the monomer contains at least one selected from acrylic compounds represented by the general formula 1.

However, R1 and R2 in a formula are a C1-C9 alkyl group which may have a hydrogen atom, a hydroxyl group, and a hydroxyl group, and m and n are integers whose sum of m and n is 14 or less. 2. The photopolymerizable composition according to claim 1, wherein the photopolymerizable monomer is an acrylic compound in which m and n in the general formula 1 are each 0. 3. The photopolymerizable composition according to claim 1, comprising at least one of a conductive inorganic material, an insulating inorganic material, and an inorganic pigment material. The photopolymerizable composition according to any one of claims 1 to 3, wherein the photopolymerizable composition is formed on a flexible film to form a photosensitive film.