JP2008195572A - Glass paste for partition in plasma display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a non-lead glass paste having a low melting point, having a low specific dielectric constant and being suitable for a partition in a plasma display. <P>SOLUTION: The glass paste containing a glass particle and an inorganic particle except glass contains a zinc oxide and a boron oxide as essential ingredients, has a thermal linear expansion coefficient of 100×10<SP>-7</SP>/K or more and has a softening temperature of lower than 600°C. The inorganic particle is at least one kind selected from the group consisting of silica, alumina and zirconia. The weight ratio of the glass particle to the inorganic particle except glass is 20/80 to 80/20. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a glass paste suitable for a partition wall of a plasma display panel.

  In recent years, plasma display panels, that is, PDPs are being widely used in the field of flat display devices such as televisions and computers. In the PDP, a large number of cells (micro discharge spaces) partitioned by partition walls are formed between two substrate glasses, a phosphor is arranged on the inner surface of each cell, and the cells are filled with a discharge gas. It has a structure, and a discharge gas is excited by an inter-electrode discharge in the cell, and a phosphor in a ground state is emitted by ultraviolet rays emitted at that time to form a pixel.

  Usually, an AC type PDP is provided with a transparent electrode and a dielectric glass layer covering the transparent electrode on one side (a surface facing the back substrate) of the front glass substrate, and on one side (a surface facing the front substrate) of the back glass substrate. A plurality of address electrodes are formed so as to be orthogonal to the transparent electrode, the entire upper surface of the substrate including the electrode portion is covered with a dielectric glass layer, and a cell is formed on the dielectric glass layer corresponding to the non-electrode portion. It is manufactured by installing barrier ribs for preventing crosstalk between them and finally arranging phosphors on the side and bottom surfaces of the barrier ribs.

Low-melting-point glass is exclusively used in the form of powder for forming each element such as a dielectric glass layer and partition walls of the PDP. That is, the low-melting glass powder is usually melted and integrated at a temperature of about 500 to 600 ° C. As the glass powder, PbO—SiO ₂ —B ₂ O ₃ -based glass containing lead has been widely used because it satisfies desired low melting point characteristics and can select a wide range of glass characteristics.

  However, the glass material has excellent properties as a glass for forming each element of this kind of PDP, but considering recent environmental problems, it contains a large amount of harmful lead components. Its use is undesirable and should be avoided. For example, when this is used for forming a partition wall by a sandblasting method, considering that about 60% of the glass is discarded together with the blasting material by applying a glass paste on the entire surface of the substrate, drying, and then blasting, There is a disadvantage in that the disposal processing requires cumbersome work and cost.

  Therefore, in the PDP industry, it is desired to develop a glass that does not contain a lead component that can replace the glass containing lead, and various lead-free glasses have been proposed in accordance with this demand.

Examples of lead-free glass compositions for PDP partition walls include Bi ₂ O ₃ —SiO ₂ glass in Patent Document 1 and Li ₂ O—B ₂ O ₃ —Al ₂ O ₃ glass in Patent Document 2. Each has been proposed.
Furthermore, in recent years, technological development for high-definition PDP has been accelerated. As the PDP is highly refined, there is a problem that the interval (pitch) between adjacent barrier ribs is narrowed and the capacitance of the panel is increased, and a low relative dielectric constant of the barrier ribs is required. Patent Document 3 proposes a phosphoric acid-based low-melting glass for a partition wall having a low relative dielectric constant, but the phosphoric acid-based low-melting glass has a problem that a large amount of gas is emitted.
JP-A-10-228869 Japanese Patent Laid-Open No. 10-167757 Japanese Patent Laid-Open No. 8-301631

  An object of the present invention is to provide glass particles that are less likely to generate cracks during firing when used for partition walls of a plasma display, and a glass paste that is suitable for partition walls of plasma displays that are less likely to cause cracks during firing. Another object of the present invention is to provide a glass paste that provides a partition wall having a low relative dielectric constant. Another object of the present invention is to provide a lead-free low melting point glass paste having a low relative dielectric constant suitable for a partition of a plasma display.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.

That is, the present invention provides [1] a glass paste for a partition wall of a plasma display comprising glass particles having a coefficient of thermal expansion of 100 × 10 ⁻⁷ / K or more and inorganic particles other than glass. [2] The content of at least one selected from the group consisting of PbO and Bi ₂ O ₃ is 5% by weight or less, the content of P ₂ O ₅ is 4% by weight or less, and thermal linear expansion The present invention provides a glass paste for partition walls of a plasma display containing glass particles having a coefficient of 100 × 10 ⁻⁷ / K or more and inorganic particles other than glass.

Furthermore, the present invention provides the following [3] to [6] as preferred embodiments according to the above [1] and [2].
[3] The glass paste for partition walls according to [1] or [2], wherein the softening temperature of the glass is less than 600 ° C.
[4] The glass paste for a partition according to any one of [1] to [3], wherein the glass contains zinc oxide and boron oxide as essential components.
[5] The glass paste for a partition wall of a plasma display according to any one of [1] to [4], wherein the weight ratio of the glass particles to inorganic particles other than the glass is 20/80 to 80/20.
[6] The glass paste for partition walls of a plasma display according to any one of [1] to [5], wherein the inorganic particles other than the glass are at least one selected from the group consisting of silica, alumina, and zirconia.
[7] A plasma display panel comprising a partition formed using the glass paste for a partition of a plasma display according to any one of [1] to [6].
[8] Glass particles for plasma display partition walls having a coefficient of thermal expansion of 100 × 10 ⁻⁷ / K or more.
[9] The content of at least one selected from the group consisting of PbO and Bi ₂ O ₃ is 5% by weight or less, the content of P ₂ O ₅ is 4% by weight or less, and the thermal expansion coefficient is Glass for manufacturing a glass paste for plasma display partition walls, which is 100 × 10 ⁻⁷ / K or more.
[10] The content of at least one selected from the group consisting of PbO and Bi ₂ O ₃ is 5% by weight or less, the content of P ₂ O ₅ is 4% by weight or less, and the thermal expansion coefficient is Use of glass of 100 × 10 ⁻⁷ / K or more for producing a glass paste for plasma display partition walls.

  If the glass particles of the present invention are used in the manufacture of plasma display partition walls, cracks during firing are less likely to occur, which is industrially useful. The partition glass paste of the present invention is used in the manufacture of plasma display partition walls. For example, since cracks during firing hardly occur, it is industrially useful, and in particular, it is industrially useful because a partition having a low relative dielectric constant can be easily formed.

In the partition wall glass particles used in the present invention, the content of at least one selected from the group consisting of PbO and Bi ₂ O ₃ is 5% by weight or less, and the content of P ₂ O ₅ is 4% by weight or less. And the coefficient of thermal expansion is 100 × 10 ⁻⁷ / K or more.

  The partition wall glass particles are mainly composed of zinc oxide and boron oxide, and the softening temperature thereof is preferably less than 600 ° C., and the softening temperature of the glass particles within the above range is obtained by firing the pattern to form partition walls. When obtained, it is preferable because firing at a lower temperature is possible.

Specifically, when glass particles having a softening temperature of less than 600 ° C. and a thermal linear expansion coefficient of 100 × 10 ⁻⁷ / K or more are exemplified, borosilicate zinc oxide calcium oxide glass particles mainly containing silicon oxide And zinc borate oxide barium oxide glass particles.
These can usually be produced by melting a raw material metal oxide, metal hydroxide, or metal carbonate at 1000 ° C. or higher.
Linear thermal expansion coefficient of the glass particles used in the present invention are ^{preferably, 100 × 10 -7 / K~300 ×} 10 -7 / K, more ^{preferably, 100 × 10 -7 / K~200 ×} 10 -7 / K, more ^{preferably, 100 × 10 -7 / K~150 ×} 10 -7 / K, even more ^{preferably, 100 × 10 -7 / K~140 ×} 10 -7 / K, and most preferably, 100 × 10 ⁻⁷ / K to 130 × 10 ⁻⁷ / K. It is preferable for the thermal linear expansion coefficient to be in the above-mentioned range because there is little shrinkage during firing and a denser partition can be obtained.
The thermal linear expansion coefficient can be generally determined according to JIS R3102: 1995, and is a value measured using a thermomechanical analyzer (TMA-8310 manufactured by Rigaku).

  Moreover, YEB2-6701 (made by Yamato Electronics Co., Ltd.) can be mentioned as a glass particle which can be obtained easily from a market. These can be used as they are, or can be used after being washed with water, pickling or solvent and then dried. Moreover, you may obtain | require the suitable average particle diameter mentioned later, and may perform a classification process using a well-known classification means.

Furthermore, the average particle diameter of the glass particle for partition used for this invention becomes like this. Preferably it is 0.01-40 micrometers, More preferably, it is 0.1-10 micrometers, Especially preferably, it is 1-8 micrometers. When the average particle size is in the above range, shrinkage during firing is small, and a denser partition wall can be obtained, which is preferable.
The average particle size is 25 ° C. using a particle size measuring device (for example, DLS-7000; manufactured by Otsuka Electronics Co., Ltd., laser diffraction / scattering particle system measuring device LA-950; manufactured by Horiba, Ltd.). It is a volume average particle diameter measured by A glass particle for a partition wall having a suitable average particle diameter may be selected and used by measuring the average particle diameter of the above-mentioned commercially available product, or for a partition wall having a suitable particle diameter range by classification means as described above. Glass particles can also be prepared.
Moreover, the shape of the glass particles for a partition of the present invention may be either spherical or crushed, but is preferably spherical.

  The partition wall glass paste of the present invention is generally used by mixing the partition wall glass particles described above with an organic vehicle to prepare a suitable paste form. Here, the organic vehicle to be used may be any of those generally used for this kind of glass paste, and these are usually made of a solvent solution of a resin. As this resin, a cellulose resin and an acrylic resin can be illustrated as a preferable thing. The cellulose resin includes ethyl cellulose, hydroxyethyl cellulose, nitrocellulose and the like, and the acrylic resin includes polybutyl acrylate, polyisobutyl methacrylate and the like. In general, the above-mentioned resin may be blended in a glass paste composition to be adjusted in a range of about 0.5 to 20% by weight of one kind alone or in combination of two or more kinds. . Further, the glass paste can be appropriately blended with additives that are usually known to be added and blended, for example, suspending agents, dispersants, adhesion improvers with substrate glass, and the like, if necessary.

  The solvent that constitutes the solvent solution of the resin may be any of various commonly known solvents and is not particularly limited. In general, those that are excellent in resin solubility and can form viscous oils are preferred. This includes medium and high boiling ester solvents, ether solvents, petroleum solvents and the like. Specific examples include ester solvents such as butyl cellosolve acetate and butyl carbitol acetate, ether solvents such as butyl carbitol, and petroleum solvents such as naphtha and mineral terpenes. These may be used alone or in combination of two or more.

The glass paste for barrier ribs of the present invention can be made into a photosensitive composition by using a photosensitive organic vehicle.
For example, the positive photosensitive composition comprises an organic component and inorganic fine particles, and the organic component contains at least an alkali-soluble resin, a photoacid generator or a photobase generator, or the organic component contains at least an alkali. It is necessary to include a resin in which a soluble group is protected with a group capable of leaving with an acid or an alkali, and to contain either a photoacid generator or a photobase generator.

  The alkali-soluble resin is not particularly limited as long as the exposed portion is alkali-soluble during development and can be eluted into an alkali developer, but mainly two types of acrylic resin and novolac resin can be preferably used.

  As the acrylic resin, for example, an acrylic resin obtained by polymerizing hydroxystyrene, acrylic acid, methacrylic acid, maleic acid, or a derivative thereof, which is a monomer having an alkali-soluble group, can be used. In addition, these alkali-soluble monomers and alkali-insoluble acrylic acid esters, methacrylic acid esters, maleic acid esters, hydroxystyrene esters, styrene, vinyl alcohol, vinyl acetate, vinyl esters, and derivatives thereof can be used in an alkaline water solution. Copolymerization may be performed as long as the property is maintained. When the alkali-soluble resin is polyhydroxystyrene, specifically, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2- (o-hydroxyphenyl) propylene, 2- (m-hydroxyphenyl) propylene, A resin obtained by polymerizing hydroxystyrenes such as 2- (p-hydroxyphenyl) propylene alone or in the presence of a radical polymerization initiator, an anionic polymerization initiator or a cationic polymerization initiator can be used.

  In addition, after polymerization, a hydrogenated product may be used in order to reduce the absorbance of the resin and improve the pattern processability. When using an acrylic resin, a preferable weight average molecular weight is 5,000-100,000 in polystyrene conversion, More preferably, it is 5,000-20,000.

  A novolak resin is also preferably used as the alkali-soluble resin. The novolak resin can be obtained by polycondensation of various phenols alone or a mixture of a plurality of them with aldehydes such as formalin and paraformaldehyde at 80 to 200 ° C. In addition, polymers obtained by partially etherifying or partially esterifying these polymers can also be used.

  Examples of phenols constituting the novolak resin include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6- Dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5- Trimethylphenol, methylene bisphenol, methylene bis p-cresol, resorcin, catechol, 2-methyl resorcin, 4-methyl resorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxy Phenol, p-methoxy Enol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α-naphthol, β-naphthol, etc. These can be used alone or as a mixture of two or more. Examples of aldehydes include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetoaldehyde, and the like, and these can be used alone or as a mixture of a plurality.

  The preferred weight average molecular weight of the novolak resin used in the positive photosensitive composition is 1,000 to 100,000, more preferably 1,500 to 25,000, and even more preferably 4,000 to 10,000 in terms of polystyrene. It is.

  A resin in which an alkali-soluble group is protected with a group capable of leaving with an acid or an alkali can also be used. When such a resin is used, a non-exposed portion is not dissolved in the developer, so that a large contrast can be obtained.

  As the resin in which the alkali-soluble group is protected with an acid or a group capable of leaving with an alkali, an acid generated from a photoacid generator or an alkali generated from a photobase generator at the time of exposure can be heated at room temperature or after exposure. Although it will not be specifically limited if it remove | eliminates by and reproduce | regenerates an alkali-soluble group, For example, a methoxymethyl group, 1-methoxyethyl group, 1-methoxypropyl group, 1-methoxybutyl group, 1-ethoxyethyl group, 1 -Acetal group such as ethoxypropyl group, 1-ethoxybutyl group, tetrahydrofuranyl group, tetrahydropyranyl group, ketal group such as 1-methoxy-1-methylethyl group, carbonate group such as t-butoxycarbonyl group, etc. is there. Of these, an acetal group is particularly preferably used. The protection of the alkali-soluble group does not need to be performed for all of the resin, and it is preferable to protect 10 to 100 mol% of the entire alkali-soluble group. It is also possible to mix 1 to 100 parts by weight of unprotected resin with 100 parts by weight of protected resin. By including such an unprotected group or resin, the sensitivity can be increased.

  The preferred weight average molecular weight of the resin in which the alkali-soluble group is protected with an acid or an alkali-eliminating group is 1,000 to 100,000, more preferably 3,000 to 50,000, still more preferably in terms of polystyrene. Is 10,000 to 30,000.

  Examples of the photoacid generator include onium salts, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, sulfonimide compounds, diazoketone compounds, and diazizonaphthoquinone compounds.

  Specific examples of the onium salt include diazonium salt, ammonium salt, iodonium salt, sulfonium salt, phosnium salt, oxonium salt and the like. Preferred onium salts include diphenyliodonium triflate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, (hydroxyphenyl) benzylmethylsulfonium toluenesulfonate Etc.

  Specific examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Preferred halogen-containing compounds include 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, and 2-naphthyl-4,6. -Bis (trichloromethyl) -s-triazine and the like can be mentioned.

  Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, and bis (2,4-xylyl). Sulfonyl) diazomethane, bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl ( And benzoyl) diazomethane.

  Specific examples of the sulfone compound include β-ketosulfone compounds and β-sulfonylsulfone compounds. Preferred compounds include 4-trisphenacyl sulfone, mesityl phenacyl sulfone, bis (phenylsulfonyl) methane, and the like.

  Examples of the sulfonate compound include alkyl sulfonate, haloalkyl sulfonate, aryl sulfonate, imino sulfonate, and the like. Specific examples of the sulfonic acid compound include benzoin tosylate, pyrogallol trimesylate, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, and the like.

  Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethyl). Sulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5 Ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (trifluoromethylsulfonyl) Oxy) naphthyl dicarboxylimide, N- (camphorsulfur Nyloxy) succinimide, N- (camphorsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyl Imido, N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] Heptane-5,6-oxy-2,3-dicarboxylimide, N- (camphorsulfonyloxy) naphthyl dicarboxylimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) Phthalimide, N- (4-methylpheny Sulfonyloxy) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) -7 -Oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy- 2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide N- (2-trifluoromethylphenylsulfonyloxy) diphe Nilmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy)- 7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6 -Oxy-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (2-fluorophenylsulfonyloxy) Phthalimide, N- (4-fluorophenylsulfonyloxy) diphenylmale N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [ 2.2.1] Hept-5-ene-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3- Examples thereof include dicarboxylimide and N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylimide.

  Specific examples of the diazoketone compound include 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds, and the like.

  From the viewpoint of pattern formation and low firing residue, diazonaphthoquinone compounds are particularly preferably used as photoacid generators, among which 1,2-naphthoquinonediazide-4-sulfonic acid and 2,3,4, Esters of 4′-tetrahydroxybenzophenone, esters of 1,2-naphthoquinonediazide-4-sulfonic acid and 1,1,1-tris (4-hydroxyphenyl) ethane, amides with diaminodiphenyl ether, etc. , 2-Naphthoquinonediazide-5-sulfonic acid with 2,3,4,4′-tetrohydroxybenzophenone, methyl gallate, ester with 1,1,1-tris (4-hydroxyphenyl) ethane, diaminodiphenyl ether, etc. Amides and the like can be mentioned as further preferred compounds.

  One kind of the photoacid generator may be used alone, or two or more kinds may be mixed and used. The mixing ratio of the photoacid generator is preferably 2 to 50 parts by weight, more preferably 100 parts by weight of an alkali-soluble resin or a resin in which an alkali-soluble group is protected with an acid or an alkali-eliminating group. Is blended at a ratio of 10 to 40 parts by weight. High contrast is achieved by setting the concentration of the photoacid generator to 2 parts by weight or more, and sensitivity can be kept high by setting it to 50 parts by weight or less.

  Examples of the photobase generator include transition metal complexes, orthonitrobenzyl carbamates, α, α-dimethyl-3,5-dimethoxybenzyl carbamates, acyloxyiminos and the like.

  Transition metal complexes include bromopentammonium cobalt perchlorate, bromopentamethylamine cobalt perchlorate, bromopentapropylamine cobalt perchlorate, hexaammonium cobalt perchlorate, hexamethylamine cobalt perchlorate Salt, hexapropylamine cobalt perchlorate and the like.

  Orthonitrobenzyl carbamates include [[(2-nitrobenzyl) oxy] carbonyl] methylamine, [[(2-nitrobenzyl) oxy] carbonyl] propylamine, [[(2-nitrobenzyl) oxy] carbonyl. ] Hexylamine, [[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2-nitrobenzyl) oxy] carbonyl] aniline, [[(2-nitrobenzyl) oxy] carbonyl] piperidine, bis [[ (2-Nitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] phenylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] toluenediamine, bis [[( 2-Nitrobenzyl) oxy] carbo Ru] diaminodiphenylmethane, [[(2,6-dinitrobenzyl) oxy] carbonyl] methylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] propylamine, [[(2,6-dinitrobenzyl) oxy ] Carbonyl] butylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] hexylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] aniline, bis [[(2,6-dinitrobenzyl) oxy ] Carbonyl] ethylenediamine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] phenylenediamine, and the like.

  Examples of α, α-dimethyl-3,5-dimethoxybenzylcarbamate include [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] methylamine, [[(α, α-dimethyl-3. , 5-dimethoxybenzyl) oxy] carbonyl] propylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] butylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl). ) Oxy] carbonyl] hexylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] cyclohexylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl Aniline, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] piperidine, [[(Α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] ethylenediamine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] hexamethylenediamine, bis [ And [(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] phenylenediamine.

  Acyloxyiminos include propionyl acetophenone oxime, propionyl benzophenone oxime, propionyl acetone oxime, butyryl acetophenone oxime, butyryl acetone oxime, adipoyl acetophenone oxime, adipoyl acetone oxime, acryloyl acetophenone oxime, alloyl benzophenone oxime, Examples include acroyl acetone oxime.

  One kind of the photobase generator may be used alone, or two or more kinds may be mixed and used. The mixing ratio of the photobase generator is preferably 2 to 50 parts by weight, more preferably 10 to 40 parts by weight based on 100 parts by weight of the resin in which the alkali-soluble group is protected with an acid or an alkali-eliminating group. It mix | blends in the ratio of a weight part. High contrast is realized by setting the concentration of the photobase generator to 2 parts by weight or more, and sensitivity can be kept high by setting it to 50 parts by weight or less.

  Furthermore, the positive photosensitive composition preferably contains an ultraviolet absorber. An ultraviolet absorber means what absorbs the wavelength of 300-400 nm, and discharge | releases the absorbed optical energy as an inactive radiation ray (thermal energy). Usually, the exposure used in the photolithography technique is performed using g-line (436 nm), h-line (405 nm), and i-line (365 nm) of an ultra-high pressure mercury lamp. Absorption by the photosensitive compound (photoacid generator, photobase generator or sensitizer) is large, the photoreaction proceeds only in the surface layer, and the reaction for image formation does not proceed in the lower layer. By adding a UV absorber into the paste, it absorbs light with wavelengths near h and i rays, thereby increasing the transmittance of g rays and promoting the photoreaction to the lower layer of the coating film of the photosensitive paste. Can do.

  Ultraviolet absorbers are particularly effective if they have excellent absorbance at wavelengths near h-line and i-line. Specific examples include benzophenone compounds, cyanoacrylate compounds, salicylic acid compounds, benzotriazole compounds, indoles. Compounds, inorganic fine particle metal oxides, and the like. Among these, benzophenone compounds, cyanoacrylate compounds, benzotriazole compounds, and indole compounds are particularly effective. Specific examples thereof include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2 -Hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4 -(2-hydroxy-3-methyl (Chryloxy) propoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2 '-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-t-butylphenyl) -5-chlorobenzo Triazole, 2- (2′-hydroxy-4′-n-octoxyphenyl) benzotriazole, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, 2-ethyl-2-cyano-3,3-diphenyl BONASORB UA-3901 (made by Orient Chemical Co., Ltd.) and BONASORB are acrylate and indole-based absorbents A-3902 (made by Orient Chemical Co., Ltd.) SOM-2-0008 (made by Orient Chemical Co., Ltd.), Basic Blue, Sudan Blue, Sudan R, Sudan II, Sudan III, Sudan IV, Oil Orange SS, Oil Violet, Oil Yellow OB (above , Aldrich Corporation) and the like. Furthermore, a methacryl group or the like may be introduced into the skeleton of these ultraviolet absorbers and used as a reaction type. In the present invention, one or more of these can be used.

  The addition amount of the ultraviolet absorber is preferably 0.001 to 10 parts by weight, and more preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the organic component excluding the solvent. By setting the addition amount of the ultraviolet absorber within this range, the contrast to the developer can be improved and the sensitivity to the exposure light can be maintained.

  The positive photosensitive composition also preferably contains a crosslinking agent. When a crosslinking agent is included, post-baking after exposure allows a crosslinking reaction between the crosslinking agent and the resin to proceed in the unexposed area, thereby improving developer resistance. As the crosslinking agent, those containing one or more ethylenically unsaturated double bonds are preferably used.

In order to increase the dissolution rate in an alkali developer, a phenol compound such as tetrahydroxybenzophenone, trihydroxybenzophenone, bisphenol A, methyl gallate, cresol, trihydroxyphenylmethane, or an organic acid such as nicotinic acid can be added.
In addition, an organic base, an organic acid, a light absorber, or the like may be added to the positive photosensitive composition in order to improve sensitivity, resolution, resistance to leaving, and the like.

  The addition amount of the organic component and the inorganic fine particles in the positive photosensitive composition is preferably 6: 4 to 1: 9 in terms of solid content not containing a solvent. More preferably, it is 4: 6 to 1: 9, and still more preferably 3.5: 6.5 to 2: 8. By keeping in this range, it is possible to obtain a positive photosensitive composition that has good pattern processability and does not generate defects during firing.

  When preparing the photosensitive paste using the glass particles for barrier ribs of this invention, content of this glass particle for barrier ribs is a mass fraction with respect to the photosensitive paste total amount, Preferably it is 5-80 mass%, More preferably, it is 10 Although the photosensitive paste using the glass particles for a partition wall of the present invention is ~ 70% by mass, even if the content is increased as compared with the conventionally disclosed photosensitive paste, a decrease in sensitivity is hardly recognized. It is effective to use in the range of preferably 10 to 70% by mass, more preferably 20 to 60% by mass. In addition, it is preferable for the content of the partition glass particles to be in the above-mentioned preferable range because the partition formed using the photosensitive paste tends to have high strength.

Further, when preparing the photosensitive paste, it is preferable to adjust the content of alkali metal oxide and alkaline earth metal oxide to 2% by mass or less with respect to the total amount of the photosensitive paste, and 1.5% by mass or less. More preferably, it is more preferably 1% by mass or less. The photosensitive paste thus obtained makes it possible to manufacture a dense partition by further suppressing the decrease in sensitivity when the glass particles are increased.
In addition, in order to make the content of the oxide in the photosensitive paste within the above range, the oxide content of the glass particles for the barrier ribs of the present invention is determined as described above, and other components constituting the photosensitive paste are further obtained. What is necessary is just to also obtain | require together the oxide content of a component, and to make it the sum total become 2 mass% or less by the mass fraction with respect to the photosensitive paste.

Next, the negative photosensitive composition will be described.
The negative photosensitive composition contains the following components (A) to (E), and includes the partition wall glass particles of the present invention as the component (A) which is a glass particle having a softening temperature of less than 600 ° C. It is preferable.
(A) Glass particles for partition walls of the present invention;
(B) an alkali-soluble resin;
(C) an organic solvent;
(D) inorganic particles having a softening temperature of 600 ° C. or higher;
(E) a compound that generates an acid upon irradiation or heating with electromagnetic radiation;

  Components other than the component (A) in the preferable negative photosensitive composition will be described.

Next, the novolac resin will be described.
Examples of the novolak resin include a phenol novolak resin and a substituted phenol novolak resin having a monovalent organic group on the phenyl ring of the phenol novolak resin.
Examples of substituted phenol novolac resins include cresol novolac resins.
Examples of the phenol novolak resin include a novolak resin obtained by polycondensation of a phenol compound represented by the formula (8) and an aldehyde compound represented by the formula (9), and hydrogen of a phenolic hydroxyl group of the novolak resin. A resin in which a part of the atoms is substituted with a monovalent organic group is exemplified.

Wherein (8), Q ¹ is an organic group of monovalent C1-20, when n is 2, two Q ¹ is may be the same or different. n represents an integer of 0 to 2.
In formula (9), Q ² represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. ]

  The monovalent organic group having 1 to 20 carbon atoms may be linear, branched or cyclic, and examples thereof include a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms and 3 to 20 carbon atoms. A branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the like. The aromatic hydrocarbon group having 6 to 20 carbon atoms may be substituted with an alkyl group, an alkenyl group or the like.

  The aromatic hydrocarbon group having 6 to 20 carbon atoms represents a group having an aromatic ring or a group in which a hydrocarbon group is substituted on the aromatic ring, and the total number of carbon atoms constituting the group is 6 to 20 It is. Examples of aromatic ring substituents include methyl groups, ethyl groups, propyl groups, isopropyl groups, n-butyl groups, tert-butyl groups and other alkyl groups, allyl groups, vinyl groups and other alkenyl groups, allyloxy groups. And alkynyloxy groups such as ethynyloxy groups, and the like.

  Specific examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl group, naphthyl group, anthryl group, tolyl group, xylyl group, trimethylphenyl group, ethylphenyl group, diethylphenyl group, triethylphenyl group, propyl A phenyl group, a butylphenyl group, a methyl naphthyl group, a dimethyl naphthyl group, a trimethyl naphthyl group, a vinyl naphthyl group, a methyl anthryl group, an ethyl anthryl group and the like can be mentioned, and a phenyl group, a tolyl group and a xylyl group are particularly preferable.

The substitution position of Q ¹ in the formula (8) is preferably one in which at least two positions are not substituted among the 2-position, 4-position and 6-position from the phenol hydroxyl group. Specific examples of the compound represented by the formula (8) include phenol o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-propylphenol, m-propylphenol, p-propylphenol, o-isopropylphenol, m-isopropylphenol, o-tert-butylphenol, m-tert-butylphenol, o-hexylphenol, m-hexylphenol, o-decylphenol, m-decyl Phenol, o-dodecylphenol, m-dodecylphenol, o-hexadecylphenol, m-hexadecylphenol, o-icosylphenol, m-icosylphenol, o-cycloheptylphenol, m-cycloheptylphenol, -Cyclohexylphenol, m-cyclohexylphenol, o-phenylphenol, m-phenylphenol, o-toluylphenol, m-toluylphenol, 2,5-xylenol, 2,3-xylenol, 3,5-xylenol, 2-ethyl -5-methylphenol, 2-ethyl-3-methylphenol, 3-ethyl-5-methylphenol, 2-isopropyl-5-methylphenol, 2-isopropyl-3-methylphenol, 3-isopropyl-5-methylphenol 2-tert-butyl-5-methylphenol, 2-tert-butyl-3-methylphenol, 3-tert-butyl-5-methylphenol, 2-hexyl-5-methylphenol, 2-hexyl-3-methyl Phenol, 3-hexyl-5 Tylphenol, 2-cyclohexyl-5-methylphenol, 2-cyclohexyl-3-methylphenol, 3-cyclohexyl-5-methylphenol, 2-phenyl-5-methylphenol, 2-phenyl-3-methylphenol, 3- Phenyl-5-methylphenol, 2-naphthyl-5-methylphenol, 2-naphthyl-3-methylphenol, 3-naphthyl-5-methylphenol, 2,5-diethylphenol, 2,3-diethylphenol, 3, 5-diethylphenol, 2,5-dipropylphenol, 2,3-dipropylphenol, 3,5-dipropylphenol, 2,5-biscyclohexylphenol, 2,3-biscyclohexylphenol, 3,5-bis Cyclohexylphenol, 2,5-diphenylphenol Examples include enol, 2,3-diphenylphenol, and 3,5-diphenylphenol.
Among them, preferably phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, 2,3-xylenol, 2-butylphenol, 2-isobutylphenol, 2-cyclohexylphenol, 2-phenylphenol is mentioned, More preferably, phenol, o-cresol, m-cresol, and p-cresol are mentioned.

The monovalent organic group having 1 to 20 carbon atoms in ^{Q 2} in the formula (9) are as defined above.
Examples of the aldehyde compound represented by the formula (9) include formaldehyde, acetaldehyde, propanal, butanal, hexanal, octanal, decanal, dodecanal, hexadecanal, icosanal, 2-methylpropanal, 2-methylbutanal, 2- Ethylbutanal, 2,2-dimethylpropanal, acrolein, 2-butenal, 2-hexenal, 2-octenal, acetylenic aldehyde, 2-butynal, 2-hexinal, 2-octynal, cycloheptylcarbalaldehyde, cyclohexylcarbal Examples include aldehyde, benzaldehyde, 1-naphthylaldehyde, 2-naphthylaldehyde, styrylaldehyde, and preferably formaldehyde and acetaldehyde. As the aldehyde compound, a depolymerizable polymer precursor can be used, and the aldehyde group may be protected with an acetal group or a hemiacetal group.

  As the formaldehyde, paraformaldehyde which is a depolymerizable polymer precursor or formalin which is an aqueous solution can be used.

The condensation method of the phenol compound represented by the formula (8) and the aldehyde compound represented by the formula (9) is not particularly limited. For example, it can be achieved by using an acid catalyst in the presence or absence of a reaction solvent. it can.
The reaction temperature is preferably 0 to 200 ° C, more preferably 50 to 150 ° C, and the reaction time is preferably 0.1 to 30 hours, more preferably 1 to 20 hours.
Examples of the acid catalyst include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, acetic acid, oxalic acid, malonic acid, and toluenesulfonic acid.

  Examples of the reaction solvent used for the condensation include alcohols such as methanol, ethanol, isopropanol, and tert-butyl alcohol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl hexyl ketone, methyl heptyl ketone, and cyclohexyl ketone; propyl acetate, butyl acetate, Esters such as isobutyl acetate, methyl propionate, ethyl lactate, propylene glycol acetate; ethers such as dibutyl ether, tetrahydrofuran, tetrahydropyran, dioxane; aromatic hydrocarbons such as benzene, toluene, xylene; dichloromethane, chloroform, four Halogenated hydrocarbons such as carbon chloride and bromoform; hydrocarbons such as hexane, heptane, decane, and petroleum ether can be used. Others can be used by mixing two or more kinds. In addition, water may coexist in the reaction system, and in the case of a solvent that is incompatible with water, a reaction solvent separated into two layers may be used. Water may be removed by distillation dehydration or the like.

  In the above examples of the condensation method, it is preferable to use ketones, esters, and aromatic hydrocarbons as a reaction solvent and to use an organic acid such as acetic acid, oxalic acid, malonic acid, toluenesulfonic acid as a catalyst.

In addition, a resin in which a part of the phenolic hydroxyl group of the novolak resin is substituted with an OQ ³ group (where Q ³ represents a monovalent organic group having 1 to 20 carbon atoms) is used as the alkali-soluble resin (C). You can also. Here, Q ³ is exemplified by the same group as Q ¹ described above. Such a resin in which a part of the phenolic hydroxyl group is substituted with an OQ ³ group is also referred to as “novolak resin” in the present invention.

Examples of the reaction for substituting a part of the phenolic hydroxyl group with OQ ³ group include sodium hydroxide, potassium hydroxide, metallic sodium, metallic lithium, metallic potassium, n-butyllithium, sodium naphthalate, sodium methoxide and the like. Using a strong alkali, the phenolic hydroxyl group can be converted into a metal phenolate group, and then the compound represented by the formula (10) can be reacted.

[In Formula (10), Q ³ is as defined above. T represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a mesyl group or a tosyl group. ]

  Examples of the compound represented by the formula (10) include methyl fluoride, ethyl fluoride, decyl fluoride, hexyl fluoride, octyl fluoride, dodecyl fluoride, hexadecyl fluoride, icosyl fluoride, methyl chloride, ethyl chloride, Decyl chloride, hexyl chloride, octyl chloride, dodecyl chloride, hexadecyl chloride, icosyl chloride, methyl bromide, ethyl bromide, decyl bromide, hexyl bromide, octyl bromide, dodecyl bromide, hexadecyl bromide, icosyl bromide, Benzyl bromide, methyl iodide, ethyl iodide, decyl iodide, hexyl iodide, octyl iodide, dodecyl iodide, hexadecyl iodide, icosyl iodide, benzyl iodide, methyl ethyl sulfonate, methyl butyl sulfonate, Methyl octyl sulfonate, methyl decyl sulfonate, toluyl ethyl sulfonate, buty Acid toluyl, octyl sulfonic acid toluyl, include decyl sulfonate toluyl is preferably methyl bromide, ethyl bromide, methyl iodide, and ethyl iodide.

The compound represented by the formula (10) is 0.001 or more and 0.99 mol equivalent or less, preferably 0.001 or more and 0.8 mol equivalent or less, with respect to 1 mol equivalent of the phenolic hydroxyl group of the novolak resin to be used. More preferably, 0.001 to 0.5 molar equivalent is used.
Here, the molar equivalent of the phenolic hydroxyl group in the novolak resin to be used can be determined using a commonly used alkali titration method.

Solvents in the reaction of the novolak resin with the compound represented by the formula (10) include alcohols such as methanol, ethanol, isopropanol and tert-butyl alcohol; methyl ethyl ketone, methyl isobutyl ketone, methyl hexyl ketone, methyl heptyl ketone, cyclohexyl Ketones such as ketones; ethers such as dibutyl ether, tetrahydrofuran, tetrahydropyran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and bromoform; Hydrocarbons such as hexane, heptane, decane, and petroleum ether can be used, and these can be used alone or in combination of two or more. In particular, ethers, aromatic hydrocarbons or halogenated hydrocarbons are preferred. In the reaction, water may coexist as long as the reactants and catalysts used are not deactivated, but a dehydrated solvent having a water content of 100 ppm or less is preferred.
The reaction time is preferably 0.1 to 20 hours, more preferably 1 to 10 hours, and the reaction temperature is −60 to 100 ° C., preferably −20 to 50 ° C.

In particular, as a novolak resin suitable as the component (C), a phenol novolak resin obtained by polymerizing a phenol compound in which Q ¹ in formula (8) is a hydrogen atom and formaldehyde, or Q ¹ in formula (8) is a methyl group. Particularly preferred is a cresol novolac resin obtained by polymerizing a phenolic compound and formaldehyde. These phenol novolak resins and cresol novolak resins can be preferably used because of high dissolution contrast during development.

  The novolak resin obtained as described above contains the catalyst or catalyst residue used in the condensation reaction or substitution reaction, the unreacted phenol compound, the unreacted aldehyde compound, or the unreacted compound represented by formula (10). It is preferable to remove. It is also preferable to remove the solvent used in the above condensation reaction or substitution reaction. However, when the same organic solvent (E) as described later is used, it may be used for the preparation of the photosensitive paste as a solution in which the alkali-soluble resin is dissolved without being removed.

  Thus, a suitable alkali-soluble resin to be applied to the negative photosensitive composition can be obtained. Particularly preferred as the alkali-soluble resin is a resin having a phenolic hydroxyl group, which is represented by the formula (3). Examples thereof include a polysiloxane resin having a hydroxyl group and the novolak resin.

  In addition, content of the component (B) in a negative photosensitive composition is a mass fraction with respect to the photosensitive paste, Preferably it is 3-30 mass%, More preferably, it is 4-20 mass%, Especially preferably, it is 5-5. 15% by mass.

Next, the component (C) organic solvent will be described.
The refractive index of the organic solvent applied to the photosensitive paste is preferably 1.4 to 1.8, more preferably 1.43 to 1.70, and particularly preferably 1.44 to 1.60. . When the refractive index of the organic solvent is in the above range, the transmittance of the film formed using the photosensitive paste tends to be high, which is preferable.
In the present invention, the refractive index of the organic solvent is measured at 25 ° C. using a refractometer (for example, RA-520N; manufactured by Kyoto Electronics Industry Co., Ltd.). The refractive index is also described in documents such as Revised 4th edition, Chemical Handbook, Fundamentals II, pages 514-520 (edited by the Chemical Society of Japan, Maruzen Co., Ltd., issued September 30, 1993).
Examples of the organic solvent having a refractive index of 1.4 to 1.8 include propylene glycol monobutyl ether (1.42), polypropylene glycol dibenzoate (1.52), 2-heptanone (1.41), and propylene glycol. Examples include methyl ether acetate (1.40), gamma-butyrolactone (1.44), 1,2-propanediol dibenzoate (1.54), polyethylene glycol dibenzoate (1.53), and preferably refractive index. Polypropylene glycol dibenzoate, γ-butyrolactone, 1,2-propanediol dibenzoate, and polyethylene glycol dibenzoate having a refractive index of 1.44 to 1.60. Polypropylene glycol dibenzoe DOO, 1,2-propanediol dibenzoate, polyethylene glycol dibenzoate.

  As content of the component (C) in the photosensitive paste of this invention, it is a mass fraction with respect to the photosensitive paste, Preferably it is 1-30 mass%, More preferably, it is 3-20 mass%, Especially preferably, it is 5-5. 15% by mass.

Next, the inorganic particles other than glass having a component (D) softening temperature of 600 ° C. or higher are preferably silica particles, titania particles, alumina particles, and the like. These inorganic particles may be used alone or in combination of two or more. As such inorganic particles, commercially available products that are readily available from the market can be used.
Examples of commercially available silica particles include Admafine (manufactured by Admatechs).
Commercially available titania particles include high-purity titanium oxide CR-EL (manufactured by Ishihara Sangyo Co., Ltd.).
Examples of commercially available alumina particles include spherical alumina CB series (manufactured by Showa Denko KK).

  In addition, about the refractive index or average particle diameter of inorganic particles other than glass used as a component (D), it is equivalent to the suitable range quoted by the glass particle for partition walls of this invention, and can suppress the light scattering at the time of exposure. Since the content of inorganic particles other than glass in the photosensitive paste can be increased in the same manner as the glass particles for barrier ribs of the present invention, it is preferable.

  Content of component (D) in the said negative photosensitive composition is a mass fraction with respect to the photosensitive paste total amount, Preferably it is 0-70 mass%, More preferably, it is 10-60 mass%, Most preferably Is 10-50 mass%.

Next, the component (E) compound that generates an acid upon irradiation with electromagnetic radiation or heating will be described.
Examples of the compound that generates an acid upon irradiation or heating with electromagnetic radiation include a photoacid generator, a photocationic polymerization initiator, and a thermal cationic polymerization initiator.
The irradiation amount when irradiating the electromagnetic radiation is not limited as long as the compound generating an acid by the irradiation of electromagnetic radiation is more than the amount generating the acid, so long as the effect of the present invention is not impaired. In addition, the heating temperature and time can be appropriately determined within a range that does not impair the effects of the present invention as long as the compound generating an acid by heating is below the temperature and time for generating an acid.
Examples of the photoacid generator include [cyclohexyl- (2-cyclohexanonyl) -methyl] sulfonium trifluoromethanesulfonate, bis (p-tolylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and tert-butylcarbonylmethyl. -Tetrahydrothiophenium trifluoromethanesulfonate etc. are mentioned. As the photoacid generator, in addition to the above, compounds described in JP-A No. 11-202495 can also be used.
Examples of the photo cationic polymerization initiator and the thermal cationic polymerization initiator include iodonium salts, sulfonium salts, phosphate salts, and antimonate salts. Specifically, Rhodesyl Photoinitiator 2074 (manufactured by Rodel), Adekaoptomer SP-150, Adekaoptomer SP-152, Adekaoptomer SP-170, Adekaoptomer SP-172, Adeka Opton CP series (any) Asahi Denka Kogyo Co., Ltd.). In addition to the above, compounds described in JP-A-9-118663 can also be used.

The content of the component (E) in the negative photosensitive composition is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass with respect to the total amount of the photosensitive paste.
When the content of the compound that generates an acid upon irradiation or heating with electromagnetic radiation is within the above range, a pattern can be formed with good productivity, which is preferable.

Moreover, the compound which generate | occur | produces the acid represented by Formula (11) by irradiation of electromagnetic rays may be contained as a component (E).

[In Formula (11), Rf represents a C1-C20 monovalent organic group substituted with a fluorine atom. ]

  As a C1-C20 monovalent organic group substituted by the fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a butyl group etc. are mentioned, for example.

As a compound which generate | occur | produces the acid represented by Formula (11) by electromagnetic irradiation, the iodonium salt of the acid represented by Formula (11), a sulfonium salt, an ester compound, etc. are mentioned, for example.
Examples of the iodonium salt of the acid represented by the formula (11) include DPI-105, DPI-109, BI-105, MPI-105, MPI-109, BBI-105, BBI-109, and BBI-110. (Both are made by Midori Chemical Co., Ltd.).

Examples of the sulfonium salt of the acid represented by the formula (11) include TPS-105, TPS-109, MDS-105, MDS-109, MDS-205, BDS-109, DTS-105, and NDS-105. NDS-155, NDS-159, NDS-165 (all of which are manufactured by Midori Chemical Co., Ltd.).

Examples of the ester compound of the acid represented by the formula (11) include NAI-105, NAI-109, NDI-105, NDI-109, SI-105, SI-109, PI-105, and PI-109. (Both are made by Midori Chemical Co., Ltd.).

Moreover, you may add the compound which has a cationic ring-opening polymerizable functional group to the said negative photosensitive composition.
Examples of the cationic ring-opening polymerizable functional group include a cyclic ether group, a cyclic acetal group, and a cyclic ester group.
Examples of the cyclic ether group include an oxetanyl group, an oxolanyl group, and an oxepanyl group.
Examples of the cyclic acetal group include a 1,3-dioxolanyl group, a 1,3,5-trioxanyl group, a 1,3-dioxepanyl group, a 1,3,6-trioxacyclooctanyl group, and the like.
Examples of the cyclic ester group include β-propiolactonyl group, δ-valerolactonyl group, ε-caprolactonyl group, glycolide group, lactide group, 2,6,7-trioxabicyclo [2,2,1] heptanyl group. And trimethylene carbonate group.
In particular, when the alkali-soluble resin is a resin having a suitable phenolic hydroxyl group, the compound having a cationic ring-opening polymerizable functional group is combined with the phenol ring of the resin having a phenolic hydroxyl group together with the cationic ring-opening polymerization, Also functions as a crosslinking agent. Particularly preferably, a compound having a cyclic ether group is preferable. Specifically, a functional group selected from the functional group represented by the formula (2) and the functional group represented by the formula (3) is contained in the molecule. A compound having a plurality is preferred. Examples of such compounds include ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,2,7,8-diepoxyoctane, neopentyl glycol diglycidyl ether, 1,4-cyclohexanedi Examples include methanol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol propoxylate triglycidyl ether, and glycerol diglycidyl ether.

Furthermore, a silicon compound having a molecular weight of 1000 or less may be added to the negative photosensitive composition as necessary.
When the compound having cationic ring-opening polymerizability is used as the silicon compound, at least one function selected from the group consisting of a functional group represented by formula (1) and a functional group represented by formula (2) A silicon compound having a group is preferred. Such a silicon compound functions as a crosslinking agent in the same manner as described above. For example, glycidyloxypropyltrimethoxysilane, glycidyloxypropyltriethoxysilane, oxetanyloxypropyltrimethoxysilane, oxetanyloxypropyltriethoxysilane, 1,3-bis (glycidyloxypropyl) -1,1,3,3, -tetramethyl-disiloxane, 1,3-dioxiranyl-1,1,3,3, -tetramethyl-disiloxane, 1,3 -Bis (oxetanyloxypropyl) -1,1,3,3, -tetramethyl-disiloxane and the like.
In addition, when a silicon compound having a carboxyl group such as 1,3-di (carboxypropyl) -1,1,3,3-tetramethyldisiloxane is used as the silicon compound, negative photosensitivity is obtained in the development described later. After the coating film made of the composition is exposed, the dissolution rate can be further improved in the dissolution part that dissolves in the developer.
When such a silicon compound is added to the negative photosensitive composition, the addition amount is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, based on the total amount of the photosensitive composition. And particularly preferably 3 to 6% by mass.

  Furthermore, additives such as a light absorber, a photosensitizer, a plasticizer, a dispersant, a suspending agent, and a leveling agent may be added to the negative photosensitive composition as necessary.

  The negative photosensitive composition can be produced by uniformly mixing and dispersing the components (A) to (E) with a three-roller or a kneader.

Next, an example is given and demonstrated about the method of patterning using the said negative photosensitive composition, but this invention is not limited to this method.
First, the negative photosensitive composition is applied over the entire surface or a part of the substrate. As a coating method, for example, a bar coater, a roll coater, a die coater, a screen printing method or the like can be used. The coating thickness can be adjusted by selecting the number of coatings and the viscosity of the paste, and is preferably about 5 to 500 μm, more preferably 50 to 200 μm.

When applying a negative photosensitive composition on a substrate, it is preferable to treat the surface of the substrate with a surface treatment liquid in order to improve the adhesion between the substrate and the coating film.
Examples of the surface treatment liquid include silane coupling agents such as glycidyloxypropyltriethoxysilane, glycidyloxypropyltrimethoxysilane, and oxetanyloxypropyltriethoxysilane. As the silane coupling agent, it is preferable to use a silane coupling agent diluted to a concentration of 0.1 to 5% with an organic solvent such as ethylene glycol monomethyl ether, methyl alcohol, ethyl alcohol, propyl alcohol, or butyl alcohol.
Examples of the surface treatment method include a method in which a surface treatment liquid is uniformly applied on a substrate with a spinner or the like and then dried at 80 to 140 ° C. for 5 to 60 minutes.
After drying, exposure is performed using an exposure apparatus. Examples of the exposure apparatus include a proximity exposure machine.
When exposing a large area, a large area can be exposed with an exposure machine having a small exposure area by applying a photosensitive paste on a substrate and then performing exposure while moving the photosensitive paste. For the exposure, for example, ultraviolet rays, electron beams, X-rays, visible light, near infrared light, or the like can be used.

Development is performed after exposure. Development is usually carried out by a dipping method, a spray method, a brush method or the like.
Examples of the developer include aqueous alkali solutions such as tetramethylammonium hydroxide, monoethanolamine, diethanolamine, sodium hydroxide, sodium carbonate, potassium hydroxide, and potassium carbonate.
The alkali concentration in the aqueous solution is preferably 0.05 to 5% by mass, more preferably 0.1 to 53% by mass. When the alkali concentration is within the above range, the removability of the portion to be developed and removed is good, and the pattern to be left is less likely to be peeled off or eroded, which is preferable.
The temperature during development is preferably 15 to 50 ° C. in terms of process control.

After the pattern is formed as described above, the partition walls can be formed by firing in a firing furnace. The firing atmosphere and firing temperature vary depending on the type of photosensitive paste and substrate, but firing is preferably performed at 400 to 600 ° C. in an atmosphere such as air or nitrogen. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used.
In particular, when patterning on a glass substrate, baking is preferably performed at a temperature of 400 to 600 ° C. for 10 to 60 minutes.

A coat layer may be formed on the surface of the obtained partition wall. The coating layer is formed by applying and drying a coating agent such as a paste agent or a ceramic coating agent composed of low melting point glass particles and a binder resin, and baking it to form on the surface of the partition wall, or after forming the pattern, the coating agent It may be formed on the surface of the partition simultaneously with the formation of the partition by baking after coating.
Examples of the low melting point glass particles include tin oxide phosphate glass, bismuth oxide glass, and lead glass.
Examples of the binder resin include butyral resin, polyvinyl alcohol, acrylic resin, and poly α-methylstyrene.
As the ceramic coating agent, an aqueous metal salt coating agent, an alkoxy metal salt coating agent, or the like can be used. Specifically, as the aqueous metal salt coating agent, MS-1700, an alkoxy metal salt coating agent is used. Examples of the agent include G-301 and G-401 (both manufactured by Nippon Ceramic Co., Ltd.).
The firing temperature of the coating layer is preferably about 250 to 600 ° C. when a paste agent composed of low-melting glass particles and a binder resin is used, and preferably 10 to 500 ° C. when a ceramic coating agent is used.

In the partition wall obtained by the above pattern processing method, the amount of change in the top width dimension, the bottom width dimension and the height dimension of the partition wall before and after firing is preferably within ± 30%, more preferably Within ± 10%.
When the change in the pattern size is in the above range, it can be suitably used as a partition wall for the back plate of the plasma display.
According to the photosensitive paste comprising the glass particles for barrier ribs of the present invention, even if the glass particle content is increased, the decrease in sensitivity during exposure can be reduced, and a pattern can be formed. For example, it is suitable for manufacturing a partition wall of a back plate of a plasma display.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, it cannot be overemphasized that this invention is not limited by these Examples.

Example 1
150 g of 50 wt% ethylene glycol diacetate solution prepared by dissolving phenol novolac resin (PSM-4326; manufactured by Gunei Chemical Industry Co., Ltd.) under a nitrogen atmosphere at 70 ° C. to 80 ° C., Rhodosyl Photoiniti Ater (PI-2074; manufactured by Rodel) 4.66 g, sensitizer (DBA; manufactured by Kawasaki Kasei Kogyo Co., Ltd.) 0.95 g, 1,3-bis (3′-glycidyloxypropyl) -1,1, 3,3-tetramethyldisiloxane (TSL-9960; manufactured by GE Toshiba Silicones) 28.11 g, polypropylene glycol dibenzoate (Aldrich) 6.21 g, 1,2-propanediol dibenzoate (Aldrich) 15.61g, ethylene glycol diacetate for viscosity adjustment (Aldrich Corp.) )) 12.43 g was put into a 500 mL eggplant flask to prepare a uniform solution, and a viscous phenol novolac resin photosensitive composition was obtained.
217.97 g of the above-mentioned phenol novolac resin photosensitive composition, spherical silica (SO-C6 + epoxy surface treatment; manufactured by Admatechs Co., Ltd.) 199.93 g, low melting point glass A (YEB2-6701; thermal expansion coefficient 105 × 10 ⁻⁷ / K Manufactured by Yamato Electronics Co., Ltd., glass composition; CaO 10%, B ₂ O ₃ 27%, ZnO 18%, BaO 45% 299.85 g, polyacrylic acid (manufactured by Aldrich Co.) 50 wt% γ-butyrolactone solution 11 A photosensitive paste was prepared by kneading 0.86 g and 8.97 g of ε-caprolactone using a ceramic three-roll mill (manufactured by Inoue Seisakusho Co., Ltd.).

The prepared photosensitive paste was applied once on a glass substrate (PD200; manufactured by Asahi Glass Co., Ltd.) using a 250 μm gap applicator. After coating, the coating film was prepared by drying for 40 minutes in a 95 ° C. far-infrared oven (small precision test furnace, manufactured by Yako Co., Ltd.).
The dried coating film was exposed by a proximity exposure machine (MAP-1300; manufactured by Dainippon Screen Mfg. Co., Ltd.) using a mask having a 30 μm line and a 160 μm pitch and a 480 μm pitch. The irradiation exposure dose was 400 mJ / cm ² . After exposure, the substrate was baked at 120 ° C. for 10 minutes, and then spray-developed using a 0.4 mass% aqueous sodium hydroxide solution (manufactured by Ninomiya System Co., Ltd.). When the obtained pattern was measured using a laser microscope (manufactured by Lasertec Corporation), a pattern having a pattern upper width of 28 μm, a pattern lower width of 88 μm, and a height of 109 μm was obtained.

  The pattern formed on the glass substrate was baked in a muffle furnace at 580 ° C. for 30 minutes, whereby a partition having a pattern upper width of 26 μm, a pattern lower width of 84 μm, and a height of 102 μm was obtained without peeling and cracking.

Example 2
Except for using low melting point glass B (YEB2-6703; coefficient of thermal expansion 110X10 ⁻⁷ / K; manufactured by Yamato Electronics Co., Ltd., glass composition: CaO 16%, B ₂ O ₃ 25%, ZnO 17%, BaO 42%) A photosensitive paste was prepared in the same manner as in Example 1.

  The obtained photosensitive paste was applied, exposed and developed on a glass substrate in the same manner as in Example 1, and a partition having a pattern upper width of 26 μm, a pattern lower width of 86 μm and a height of 102 μm was peeled off and obtained without cracks.

Comparative Example 1
Low melting point glass C (YEB2-5701; coefficient of linear thermal expansion 75X10 ^-7 / K; Yamato Electronic Co., Ltd., glass _{composition; CaO 17%, B 2 O} 3 33%, 50% ZnO) except for using the implementation A photosensitive paste was prepared in the same manner as in Example 1.

  When the obtained photosensitive paste was applied to a glass substrate, exposed, developed and baked in the same manner as in Example 1, cracks were partially generated, and good partition walls could not be obtained.

  The glass paste of the present invention can be used for forming a partition for a back plate as a member of a plasma display, etc., and can be expected to be used for forming a spacer for a flat backlight, a microreactor and the like.

Claims (10)

A glass paste for a partition wall of a plasma display, comprising glass particles having a thermal linear expansion coefficient of 100 × 10 ⁻⁷ / K or more and inorganic particles other than glass. The content of at least one selected from the group consisting of PbO and Bi ₂ O ₃ is 5% by weight or less, the content of P ₂ O ₅ is 4% by weight or less, and the coefficient of thermal expansion is 100 × 10 ^A glass paste for a partition wall of a plasma display, comprising glass particles of ⁻⁷ / K or more and inorganic particles other than glass.   The glass paste for partition walls of a plasma display according to claim 1 or 2, wherein the glass has a softening temperature of less than 600 ° C.   The glass paste for partition walls of a plasma display according to any one of claims 1 to 3, wherein the glass contains zinc oxide and boron oxide as essential components.   The glass paste for plasma display partitions according to any one of claims 1 to 4, wherein a weight ratio of the glass particles to inorganic particles other than the glass is 20/80 to 80/20.   The glass paste for partition walls of a plasma display according to any one of claims 1 to 5, wherein the inorganic particles other than the glass are at least one selected from the group consisting of silica, alumina, and zirconia.   The plasma display panel provided with the partition formed using the glass paste for the partitions of the plasma display as described in any one of Claims 1-6. Glass particles for plasma display partition walls having a thermal linear expansion coefficient of 100 × 10 ⁻⁷ / K or more. The content of at least one selected from the group consisting of PbO and Bi ₂ O ₃ is 5% by weight or less, the content of P ₂ O ₅ is 4% by weight or less, and the coefficient of thermal expansion is 100 × 10 Glass for manufacturing a glass paste for plasma display partition, which is ⁻⁷ / K or more. The content of at least one selected from the group consisting of PbO and Bi ₂ O ₃ is 5% by weight or less, the content of P ₂ O ₅ is 4% by weight or less, and the coefficient of thermal expansion is 100 × 10 ^{Use of} glass having ⁻⁷ / K or more for production of glass paste for plasma display partition walls.