KR101711066B1 - Light-sensitive paste, method for forming pattern, and method for producing flat display panel member - Google Patents

Abstract

A photosensitive paste containing an ultraviolet absorber effective for forming a partition wall having a narrowest width at the top, wherein the ultraviolet absorber does not precipitate even when the paste is stored at a low temperature.
[Solution]
A photosensitive paste comprising an inorganic component containing a low-softening point glass powder, a photosensitive organic component, a compound having a structure represented by the following general formula (1), a photopolymerization initiator, and a solvent. (Wherein, R ₁ ~R ₄ are each a hydrogen atom, any one of 1 to 10 carbon atoms an alkyl group or an alkoxy group, a hydroxyl group, and a hydroxyl group with at least 1. In addition, R ₅ ~R ₈ each is hydrogen An alkyl group having 1 to 10 carbon atoms, or a halogen atom)

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive paste, a method of forming a pattern, and a method of manufacturing a member for a flat display panel,

The present invention relates to a photosensitive paste suitable for forming a pattern used for a flat display member such as a plasma display panel, a field emission display, a fluorescent display tube, etc., a method of forming a pattern using the same, and a method of manufacturing a member for a flat display panel .

Recently, the development of flat displays such as a plasma display, a field emission display, a fluorescent display tube, a liquid crystal display, an organic electroluminescence display, and a light emitting diode display has been actively conducted. In the plasma display, a plasma discharge is generated between a cathode electrode and an opposing anode electrode in a discharge space provided between a front glass substrate and a rear glass substrate, and ultraviolet rays generated from the gas sealed in the discharge space are emitted in a discharge space And the phosphor is illuminated by being irradiated to perform display. In the field emission display, display is performed by irradiating electrons emitted with an electric field to the phosphors.

A gas discharge type display such as a plasma display or a fluorescent display tube requires an insulating partition wall for separating a discharge space. In addition, the field emission display requires an insulating barrier for separating the gate electrode and the cathode. In addition, it has been reported that, in the field emission display, particularly the surface conduction electron-emitting device display, the color mixing of light emission can be suppressed by providing barrier ribs on the face plate side. In the formation of insulating barrier walls such as plasma display panels and field emission displays, materials and processing methods capable of patterning inorganic materials such as glass powder with high precision are required. As a method of processing fine patterns of such an inorganic material, a method of forming a pattern by a photosensitive paste method has been proposed (for example, Patent Documents 1 to 3).

In order to improve the quality of the display, it is desirable that the width of the uppermost part of these display barrier ribs is narrow. However, since the photosensitive paste coating film contains a large amount of inorganic fine particles dispersed therein, there is a problem that scattering of exposure light is difficult to avoid, and widening of the uppermost width due to light scattering near the surface is likely to occur. In order to solve this problem, an ultraviolet absorber having an extinction coefficient at a wavelength of 365 nm that is larger than an extinction coefficient at a wavelength of 405 nm and an extinction coefficient at a wavelength of 436 nm is added to form a partition wall having a narrowest width at the top (Patent Document 4).

Japanese Patent No. 3249576 (Claim 1) Japanese Patent No. 3239759 (Claim 1) Japanese Patent No. 3402070 (Claim 1) Japanese Patent Application Laid-Open No. 2008-224940

 However, the ultraviolet absorber disclosed in Patent Document 4 partially precipitates as crystals when the photosensitive paste is stored at a low temperature, and since this crystal becomes a scattering source of exposure light, defects are generated in the pattern formation by the photosensitive paste method And this crystal is removed in the firing process, leaving a space after removal, resulting in the problem that defects or cavities are generated in the partition wall. SUMMARY OF THE INVENTION Accordingly, the present invention is directed to a photosensitive paste containing an ultraviolet absorber effective for forming a partition wall having a narrow width at the top, wherein the ultraviolet absorber is not precipitated even when the paste is stored at a low temperature.

In order to solve the above problems, the present invention has the following configuration. That is, an inorganic component containing a low-softening point glass powder, a photosensitive organic component, a compound having a structure represented by the following general formula (1), a photopolymerization initiator, and a solvent.

(Wherein, R ₁ ~R ₄ are each a hydrogen atom, any one of 1 to 10 carbon atoms an alkyl group or an alkoxy group, a hydroxyl group, and a hydroxyl group with at least 1. In addition, R ₅ ~R ₈ each is hydrogen An alkyl group having 1 to 10 carbon atoms, or a halogen atom)

(Effects of the Invention)

According to the present invention, a photosensitive paste containing an ultraviolet absorber effective for forming a partition wall having a narrower top width can provide a photosensitive paste in which the ultraviolet absorber is not precipitated even if the paste is stored at a low temperature.

The inventors of the present invention have conducted intensive studies on a photosensitive paste in which the ultraviolet absorber does not deposit even when the paste is stored at a low temperature as a photosensitive paste containing an ultraviolet absorber effective for forming a partition wall having a narrow width at the top. .

The photosensitive paste is applied onto a substrate and, if necessary, dried to form a coating film. The exposed portion is insoluble in the developer by irradiating (exposing) the actinic ray. Then, only the non-irradiated portion is removed by the developer, It is a paste that can be done. As used herein, the term " active ray " refers to an electromagnetic wave in a wavelength range of 250 to 1100 nm. Specifically, ultraviolet ray such as ultrahigh pressure mercury lamp or metal halide lamp, visible light such as halogen lamp, helium- A laser beam of a specific wavelength such as an ion laser, a semiconductor laser, a YAG laser, or a carbon dioxide gas laser may be exemplified. Of these, ultraviolet rays with high energy are preferable.

The photosensitive paste of the present invention contains a low-softening point glass powder as an essential component as an inorganic component. By containing the low-softening point glass powder, it is baked at a temperature equal to or higher than the softening point of the low-softening point glass powder, and an organic component such as a photosensitive organic component to be described later is removed to obtain a pattern composed of an inorganic component. In the present invention, the glass having a low softening point means glass having a softening point in the range of 400 to 700 占 폚. Since the softening point is in the above-mentioned range, the meltability at the time of sintering becomes suitable in the manufacturing process of the member for a flat display panel. The range of the softening point is more preferably 500 to 650 占 폚. In the present invention, the softening point of the glass is defined as the third inflection point of the differential thermal calorimetry (DTA) curve of the glass powder. The proportion of the inorganic component of the low-softening point glass powder is preferably 60 to 95% by volume. When the content ratio is less than 60% by volume, sintering at the time of firing becomes difficult and the porosity of the pattern after firing tends to become large, which is not preferable. When it is larger than 95% by volume, the fluidity of the entire inorganic component at the time of firing becomes large, and therefore, it is not preferable because control of the pattern shape after firing becomes difficult.

The refractive index of the low-softening point glass powder is preferably 1.50 to 1.65. By using such low-softening point glass powder, the difference in the refractive index between the inorganic component and the organic component is reduced to suppress the light scattering, thereby facilitating high-precision pattern processing. The particle diameter of the low-softening point glass powder is selected in consideration of the shape of the pattern to be produced. However, the particle diameter of the low-softening point glass powder is not limited to the weight distribution curve measured by a particle size distribution measuring apparatus (e.g., "MT3300" manufactured by Nikkiso Co., Ltd.) 50% particle diameter d ₅₀ (average particle size) in the 0.1~3.0㎛, it is preferable that the maximum particle size d _max (column size) or less 10㎛.

The low-softening point glass powder which can be preferably used has the following composition, for example, as an oxide notation.

At least one of lithium oxide, sodium oxide, and potassium oxide: 3 to 15 mass%

Silicon oxide: 5 to 40 mass%

Boron oxide: 20 to 50 mass%

Zinc oxide: 0.5 to 20 mass%

Aluminum oxide: 10 to 25 mass%

Magnesium oxide and / or calcium oxide: 2 to 15 mass%

Barium oxide and / or strontium oxide: 2 to 15 mass%

As described above, at least one of alkali metal oxides of lithium oxide, sodium oxide or potassium oxide is used, and the total amount thereof is preferably 3 to 15 mass%, more preferably 3 to 10 mass%. Specific examples thereof include a mixture of 7 mass% lithium oxide, 22 mass% silicon oxide, 33 mass% boron oxide, 3 mass% zinc oxide, 19 mass% aluminum oxide, 6 mass% magnesium oxide, 5 mass% calcium oxide and 5 mass% , But the present invention is not limited thereto.

In the present invention, a filler component other than the low-softening point glass powder may be added as an inorganic component. The filler component in the present invention is added to improve the strength and plastic shrinkage of the pattern and refers to inorganic fine particles having a softening point or melting point of 700 DEG C or less which is difficult to melt and flow even at a firing temperature. By adding the filler component, shrinkage of the pattern due to firing can be suppressed and the strength of the pattern can be improved. As the filler component, those having an average particle diameter (d ₅₀ ) of 1 to 4 μm and an average refractive index of 1.4 to 1.7 can be preferably used in consideration of the dispersibility into the photosensitive paste, the filling property, and the suppression of light scattering upon exposure. In the present invention, at least one selected from the group consisting of high softening point glass powder having a softening point exceeding 700 캜 and ceramics powder such as cordierite and silica can be used as the filler component. However, it is preferable that the average particle diameter and the average refractive index The use of a high softening point glass powder is preferable.

When a high softening point glass powder is used as the filler component, it is preferable to add the glass powder having a softening point higher than 700 ° C. and lower than or equal to 1300 ° C. in a composition range of 3 to 40% by volume based on the total inorganic microfine particle. When it is less than 3 vol%, the edge of the pattern tends to collapse at the time of firing, and a pattern with good shape can not be obtained. If it is more than 40% by volume, the compactness of the pattern to be formed tends to decrease, which is not preferable. The high softening point glass powder which can be preferably used is, for example, 1 mass% of sodium oxide, 40 mass% of silicon oxide, 10 mass% of boron oxide, 33 mass% of zinc oxide, 4 mass% of zinc oxide, And 3% by mass of titanium. However, the present invention is not limited thereto.

In the present invention, it is preferable that the inorganic component is contained in the solid content of the photosensitive paste at a content of 40 to 65% by volume. Here, the solid content means a component other than the solvent contained in the paste, i.e., an inorganic component and an organic component excluding a solvent. When the content of the inorganic component is less than 40% by volume, shrinkage of the pattern due to firing tends to increase and the shape tends to become poor, which is not preferable. On the other hand, if it is larger than 65% by volume, the crosslinking reaction by exposure tends to become insufficient, and pattern formation tends to become difficult, which is not preferable.

The content ratio (volume%) of the inorganic component in the solid content can be controlled to the addition amount (mass%) in consideration of the specific gravity of the inorganic component and the organic component at the time of preparing the paste. As a method for analyzing the content of the inorganic component, there may be mentioned a method of obtaining the TGA by measuring the specific gravity of the thermogravimetric analysis (TGA) and the baking film of the inorganic component, or the method of applying the photosensitive paste, And a method of obtaining by analysis can be exemplified. For example, when 10 mg of a photosensitive paste is used as a sample and a change in weight from room temperature to 600 캜 is measured by TGA (for example, "TGA-50" manufactured by Shimadzu Corporation) Quot;). Since the solvent in the paste is usually evaporated at 100 to 150 캜, the mass ratio between the inorganic component and the organic component is obtained from the ratio of the weight after heating to 600 캜 with respect to the weight after evaporation of the solvent. On the other hand, if the specific gravity of the inorganic component is evaluated based on the film thickness, area and mass of the fired film, the content ratio can be evaluated. When the content ratio is determined by transmission electron microscope observation, a cross section perpendicular to the film surface of the paste dry film is observed by a transmission electron microscope (for example, "JEM-4000EX" manufactured by JEOL Ltd.) Image analysis may be performed by distinguishing an inorganic component from an organic component. As an evaluation region of the transmission electron microscope, for example, an area of about 20 占 퐉 占 100 占 퐉 may be observed at about 1000 to 3000 times.

The organic component of the present invention contains as essential components a photosensitive organic component selected from at least one of a photosensitive monomer, a photosensitive oligomer and a photosensitive polymer, a compound having a structure represented by the general formula (1), a photopolymerization initiator, and a solvent, An additive component such as a non-photosensitive polymer component, an antioxidant, a plasticizer, a thickener, a dispersant, and a precipitation inhibitor, if necessary.

As the photosensitive polymer, an alkali-soluble polymer can be preferably used. Since the polymer has alkali solubility, an alkaline aqueous solution can be used as a developing solution, not an organic solvent having a problem with the environment. As the alkali-soluble polymer, an acrylic copolymer can be preferably used. The acrylic copolymer is a copolymer containing at least an acrylic monomer in a copolymerization component, and specific examples of the acrylic monomer include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, Acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, allyl acrylate, benzyl acrylate, butoxy ethyl acrylate, butoxy triethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl Acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, 2 - hydroxypropyl acrylate, isodecyl acrylate, iso Acrylate, stearyl acrylate, stearyl acrylate, stearyl acrylate, stearyl acrylate, stearyl acrylate, stearyl acrylate, stearyl acrylate, stearyl methacrylate, Acrylic monomers such as fluoroethyl acrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, thiophenol acrylate and benzyl mercaptan acrylate, Acrylate, methacrylate, and the like. As the copolymerization component other than the acrylic monomer, a compound having a carbon-carbon double bond can be used, and preferably styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1-vinyl-2-pyrrolidone, and the like.

In order to impart an alkali solubility to the acrylic copolymer, unsaturated carboxylic acid or other unsaturated acid is added as a monomer. Specific examples of the unsaturated acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetate, and their acid anhydrides. It is preferable that the acid value of the polymer after the addition is in the range of 50 to 150.

In order to increase the reaction rate of the curing reaction by exposure of the acrylic copolymer, it is preferable to use an acrylic copolymer having a side chain or a carbon-carbon double bond at the molecular end. Examples of the group having a carbon-carbon double bond include a vinyl group, an allyl group, an acryl group, and a methacryl group. The acrylic copolymer having such a functional group at the side chain or at the molecular end is preferably a compound having a glycidyl group or an isocyanate group and a carbon-carbon double bond with respect to a mercapto group, an amino group, a hydroxyl group or a carboxyl group in the acrylic copolymer, Which may be synthesized by the reaction of a compound of formula

Examples of the compound having a glycidyl group and a carbon-carbon double bond include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotyl glycidyl ether, glycidyl glycol Tolylate, glycidyl isocrotonate, and the like. Examples of the compound having an isocyanate group and a carbon-carbon double bond include acryloyl isocyanate, methacryloyl isocyanate, acryloyl ethyl isocyanate, and methacryloyl isocyanate.

The photosensitive monomer is a compound containing a carbon-carbon unsaturated bond, and specific examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec- , Isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, allyl acrylate, benzyl acrylate, butoxy ethyl acrylate, butoxy triethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate , Dicyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, Isopropyl acrylate, butyl acrylate, butyl acrylate, isopropyl acrylate, Methacryloxypropyl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxy diethylene glycol acrylate, octafluoropentyl acrylate, phenoxy ethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, allyl Butylene glycol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol di Acrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, ditrimethylol propane tetraacrylate, glycerol diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol Diacrylate, triglycerol diacrylate, tri Naphthyl acrylate, 2-naphthyl acrylate, 2-naphthyl acrylate, 2-naphthyl acrylate, 2-naphthyl acrylate, 2-ethylhexyl acrylate, Bisphenol A diacrylate, diacrylates of bisphenol A-ethylene oxide adducts, diacrylates of bisphenol A-propylene oxide adducts, thiophenol acrylate, benzylmercaptan acrylate, and 1 to 5 A monomer in which a dog is substituted with a chlorine or bromine atom or a monomer having a substituent such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, chlorinated styrene, brominated styrene, , Chloromethylstyrene, hydroxymethylstyrene, carboxymethylstyrene, vinylnaphthalene, vinyl anthracene, vinyl Methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone, and the like can be given as examples of the compound . In the polyfunctional monomer, the group having an unsaturated bond may contain an acryl group, a methacryl group, a vinyl group and an allyl group. In the present invention, one or more of these may be used.

The photosensitive paste used in the present invention preferably further contains a urethane compound. The reason for this is that the incorporation of the urethane compound improves the flexibility of the paste-dried film, thereby reducing the stress at the time of firing and effectively suppressing defects such as cracking and breaking. Further, the inclusion of the urethane compound improves the thermal decomposition property and makes it difficult to generate fired residues in the firing process. As the urethane compound preferably used in the present invention, for example, a compound having a structure represented by the following general formula (2) can be exemplified.

Here, R ₉ and R ₁₀ are selected from the group consisting of a substituent containing an ethylenic unsaturated group, hydrogen, an alkyl group having 1 to 20 carbon atoms, an allyl group, an aralkyl group, and a hydroxyaralkyl group, and may be the same or different. R ₁₁ is an alkylene oxide group or an alkylene oxide oligomer, and R ₁₂ is an organic group containing a urethane bond. n is an integer of 1 to 10;

As such a urethane compound, a compound containing an ethylene oxide unit is preferable. (2) wherein R ₁₂ is an oligomer comprising an ethylene oxide unit (hereinafter referred to as EO) and a propylene oxide unit, and the EO content in the oligomer is within a range of 8 to 70 mass% to be. Since the EO content is 70 mass% or less, the flexibility is further improved and the firing stress can be reduced, so that defects can be effectively suppressed. In addition, the pyrolysis property is improved and it becomes difficult to generate fired residues in the subsequent firing process. Further, since the EO content is 8% or more, compatibility with other organic components is improved.

It is also preferable that the urethane compound has a carbon-carbon double bond. The carbon-carbon double bond of the urethane compound reacts with the carbon-carbon double bond of the other crosslinking agent to be contained in the crosslinked product, thereby further suppressing the polymerization shrinkage.

Specific examples of the urethane compound preferably used in the present invention include UA-2235PE (molecular weight 18000, EO content 20%), UA-3238PE (molecular weight 19000, EO content 10%), UA- 3348PE (molecular weight 22000, EO content 15% , UA-5348PE (molecular weight: 39000, EO content: 23%) (manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like. These compounds may be mixed and used.

The content of the urethane compound is preferably 0.1 to 10 mass% of the organic component excluding the solvent. When the content is 0.1% by mass or more, the flexibility of the paste-dried film can be improved and the firing shrinkage stress at the time of baking the paste-dried film can be relaxed. When the content exceeds 10% by mass, the dispersibility of the organic component and the inorganic component decreases, and the concentration of the monomer and the photopolymerization initiator is relatively decreased, so that defects tend to occur.

It is essential that the photosensitive paste of the present invention contains a compound having the structure represented by the general formula (1). The compound having a structure represented by the general formula (1) is an ultraviolet absorber. By containing such a compound, the width of the uppermost part of the partition wall can be narrowed (narrowed). Further, since the width of the uppermost part of the partition wall becomes narrower as the amount of the compound having the structure represented by the general formula (1) is increased, the structure shown by the general formula (1) in the photosensitive paste, The width of the uppermost part of the partition wall can be controlled by adjusting the content of the compound. Although the mechanism of the ultraviolet light of the barrier rib top is not clear, the compound having the structure represented by the general formula (1) effectively absorbs light of short wavelength such as i-line (wavelength 365 nm) which is liable to be scattered strongly upon exposure, It is presumed that the scattered light on the surface of the paste coating film is absorbed and the top width becomes thinner. Further, since the compound having the structure represented by the general formula (1) exhibits high compatibility with the photosensitive paste even at a low temperature, the photosensitive paste can be stably stored without being precipitated as crystals during low-temperature storage, It is possible to form the barrier ribs without generating defects caused by crystals precipitated in the paste or the like when the barrier ribs are formed using the subsequent photosensitive paste. Compounds having a structure represented by the general formula (1) can be added in a sufficient amount in the photosensitive paste, so that the width of the uppermost part of the partition walls can be made wider in comparison with other ultraviolet absorbers. In the photosensitive paste, The width of the uppermost part of the partition wall can be controlled in a wide range by adjusting the content of the compound having a structure represented by the formula

In the compound having the structure represented by the general formula (1), R_One~ R₄ The number of hydroxyl groups is not particularly limited as long as it is one or more, but R_One~ R₄of A compound in which one of them is a hydroxyl group and the other three are hydrogen is suitably used in the present invention. Also, R₅~ R₈All of which are hydrogen, or R₅, R₇, R₈Is hydrogen, R₆This chlorine compound is suitably used in the present invention. Such compounds include 2- (2,3-dihydroxyphenyl) -2H-benzotriazole, 2- (2,4-dihydroxyphenyl) -2H-benzotriazole, 2- (2,6-dihydroxyphenyl) -2H-benzotriazole, and R < 2 >₆, And the like. Of these, 2- (2,4-dihydroxyphenyl) -2H-benzotriazole can be preferably used.

The addition amount of the compound having the structure represented by the general formula (1) is preferably 0.1 to 20 mass% with respect to the total weight of the paste. When the content is less than 0.1% by mass, the effect of topping up is not obtained sufficiently, which is not preferable. At 20 mass% or more, the light absorption by the compound having the structure represented by the general formula (1) is not preferable because the amount of exposure required for pattern formation by the photosensitive paste method becomes too large. A more preferable range of the addition amount is 0.5 to 8 mass%.

The photosensitive paste of the present invention is required to contain a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical initiator that generates a radical by irradiation with an active light source. Specific examples thereof include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamino) benzophenone, Benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-diethoxyacetophenone, Dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, Benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butyl anthraquinone, 2-amylanthraquinone, β- Benzene anthrone, dibenzosuberone, methylene anthrone, 4-azidobenzalacetophenone, 2,6-bis (p- (Benzylidene) cyclohexanone, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 1-phenyl-1,2-butanedione 2- (O- methoxycarbonyl) Oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1,3-diphenylpropanetri- 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, naphthalenesulfonyl chloride, quinoline sulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyl A light reducing pigment such as rhenitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenylsulfone, benzoin peroxide, eosin and methylene blue, and ascorbic acid, A combination of a reducing agent such as triethanolamine, and the like. Two or more of these may be used in combination. Among them, photosensitive paste to which 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone is added in particular has high sensitivity and can reduce the amount of exposure at the time of pattern formation. Is preferably used. The photosensitive paste to which 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone is added has a particularly high sensitivity to i-line, But it is possible to form a partition wall having a narrowest top width by using it in combination with a compound having a structure represented by the above-mentioned general formula (1). The photopolymerization initiator is added in an amount of 0.05 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total amount of the photosensitive monomer and the photosensitive polymer. If the amount of the photopolymerization initiator is too small, the photosensitivity may be poor, which is not preferable. If the amount of the photopolymerization initiator is too large, the absorption of light becomes too large, so that light does not reach the core portion and the curing of the core portion becomes insufficient.

The photosensitive paste of the present invention is required to contain a solvent. As the solvent, it is particularly preferable to use a solvent whose solubility parameter is within the range of 18 to 30 MPa < ^{1/2 &} gt ;. Herein, the solubility parameter (SP value) is a solubility parameter of Hildebrandt, and specific values are described in 1999 by John Wiley & Sons, J. Braundrup, EHImmergut, EAGrulke, Polymer Handbook 4th Edition, Section VII, To Table 6 of < RTI ID = 0.0 > Of a solvent having the SP value in the range of ^1/2 18~30M㎩ example mesitylene (SP value: 18.0M㎩ ^1/2), ethylene glycol methyl ether acetate (SP value: 18.8M㎩ ^1/2), 3- Methyl-1-butanol (SP value: 19.0Mpa ^1/2 ), terpineol (SP value: 21.8Mpa ^1/2 ), benzyl alcohol (SP value: 24.8Mpa ^1/2 ) , γ- butyrolactone (SP value: 25.8M㎩ ^1/2), propiolactone (SP value: 27.2M㎩ ^1/2), ethylene glycol: to illustrate the like (SP value 29.9M㎩ ^1/2) . Of these,? -Butyrolactone is particularly preferably used in the present invention. In the present invention, a plurality of the above solvents may be mixed and used. In addition, it is also possible to combined use of a solvent other than the above, but if outside the range of the SP value is 18~30M㎩ ^1/2 of the solvent to be used in combination has the added weight of the solvent is within a range of solubility parameter is 18~30M㎩ ^1/2 Is less than the total added weight.

The photosensitive paste of the present invention may contain a non-photosensitive polymer component, for example, a cellulose compound such as methyl cellulose, ethyl cellulose, a high molecular weight polyether, or the like.

It is also preferable to add an antioxidant. The antioxidant is one having at least one of a radical chain inhibition action, an elimination action of triplet and a decomposition action of hydroperoxide. When the antioxidant is added to the photosensitive paste, the antioxidant captures the radicals, or the energy state of the excited photopolymerization initiator is returned to the ground state, so that the extra photoreaction due to the scattered light is suppressed and the amount of exposure The photoresponsive reaction occurs rapidly, so that the contrast of dissolution and insolubility in the developer can be increased. Specific examples thereof include p-benzoquinone, naphthoquinone, p-xyloquinone, p-toluoquinone, 2,6-dichloroquinone, 2,5-diacetoxy-p-benzoquinone, di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, di-t-butyl-p-cresol, hydroquinone, p-benzoquinone, Monomethyl ether, alpha -naphthol, hydrazine hydrochloride, trimethylbenzylammonium chloride, trimethylbenzylammonium oxalate, phenyl- beta -naphthylamine, parabensilaminophenol, di- beta -naphthylparaphenylenediamine, dinitrobenzene, (4-t-octylphenolate) -2- (4-t-octylphenolate) -2- (4-tert-butylphenolate) Butylphenol), 2,2'-methylenebis- (4-methyl-6-t-butylphenol), ethylhexylaminnickel- (II), 4,4'- , Triethylene glycol Bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol- -Hydroxyphenyl) propionate], 1,2,3-trihydroxybenzene, and the like, but are not limited thereto. These may be used in combination of two or more. The amount of the antioxidant added is preferably in the range of 0.1 to 30 mass%, more preferably 0.5 to 20 mass%, in the photosensitive paste. By keeping the addition amount of the antioxidant within this range, the photosensitivity of the photosensitive paste can be maintained and the contrast of the exposed portion and the non-exposed portion can be increased while maintaining the degree of polymerization and maintaining the pattern shape.

The photosensitive paste preferably used in the present invention is a paste containing a low-softening point glass powder, a photosensitive organic component, a compound having a structure represented by the general formula (1), a photopolymerization initiator, a solvent, an unexposed photosensitive polymer component, an ultraviolet absorber, Is kneaded by using a kneading machine such as a three-end roller, and homogeneously dispersed. It is also preferable that the kneaded photosensitive paste is appropriately filtered and defoamed.

The photosensitive paste thus obtained is coated on the glass substrate, exposed, developed, and fired to produce a member for a flat display panel having a partition wall having the narrowest width.

Hereinafter, a manufacturing method of a member for a flat panel display panel of the present invention will be described by taking an AC type plasma display as an example.

The plasma display is formed by sealing the front plate and the rear plate so that the front plate or the rear plate or a phosphor layer formed on both sides thereof face the inner space, and a discharge gas is sealed in the inner space. On the front panel, transparent electrodes (sustain electrodes, scan electrodes) for display discharge are formed on the substrate on the display surface side. It is preferable that the gap between the sustain electrode and the scan electrode be relatively narrow for discharging. A bus electrode may be formed on the rear surface side of the transparent electrode for the purpose of forming an electrode having a lower resistance. However, since the bus electrodes are made of Ag, Cr / Cu / Cr or the like, many of them are opaque. Therefore, unlike the transparent electrode, it is preferable that the transparent electrode is provided on the outer edge of the display surface in order to interfere with the cell display. In the case of an AC type plasma display, a transparent dielectric layer and an MgO thin film are often formed as an upper layer of the electrode. An electrode (address electrode) for address selection of a displayed cell is formed on the back plate. The partition or the phosphor layer for separating the cells may be formed on one or both of the front plate and the back plate, but is often formed only on the back plate. In the plasma display, the front plate and the rear plate are sealed, and a discharge gas such as Xe-Ne or Xe-Ne-He is sealed in the inner space between them.

A method of manufacturing the back plate will be described below. As the glass substrate, "PP8" (product of Nippon Electric Glass Co., Ltd.) or "PD200" (product of Asahi Glass Co., Ltd.) which is heat-resistant glass for soda glass or plasma display can be used. The size of the glass substrate is not particularly limited, and a thickness of 1 to 5 mm can be used. A stripe-shaped conductive pattern for address electrodes is formed on the glass substrate by a metal such as silver, aluminum, chromium, or nickel. As a forming method, a method of screen printing a metal paste containing a powder of these metals and an organic binder as a main component by screen printing, or a method of applying a photosensitive metal paste using a photosensitive organic component as an organic binder, followed by pattern exposure using a photomask, And dissolving in a developing process and heating and firing at 350 to 600 캜 to form an electrode pattern. It is also possible to use an etching method in which chromium or aluminum is vapor-deposited on a glass substrate, a resist is applied, a resist is pattern-exposed and developed, and then an unnecessary portion is removed by etching.

It is also preferable to dispose a dielectric layer on the address electrode. By providing the dielectric layer, it is possible to improve the stability of the discharge and to prevent the collapse and separation of the barrier ribs formed in the upper layer of the dielectric layer. Examples of the method for forming the dielectric layer include a method of printing or applying the dielectric paste containing an inorganic component such as a low softening point glass powder or a high softening point glass powder and a dielectric paste containing an organic binder as a main component with a screen printing method or a slit die coater.

Next, a method of forming the barrier ribs using the photosensitive paste of the present invention will be described. The barrier rib pattern is not particularly limited, but a stripe shape or a lattice shape is preferable. First, a photosensitive paste for a barrier rib is coated on a substrate on which a dielectric layer is formed. As a coating method, a method such as a bar coater, a roll coater, a slit die coater, a blade coater, and a screen printing method can be used. The coating thickness can be determined in consideration of the height of a desired partition wall and the shrinkage ratio due to baking of the paste. The coating thickness can be adjusted by the number of application, the mesh of the screen, the viscosity of the paste, and the like.

After the applied photosensitive paste is dried, exposure is performed. The exposure is generally performed by exposure through a photomask as is done by conventional photolithography. Also, a method of directly imaging with a laser beam or the like without using a photomask may be used. As the exposure apparatus, a stepper exposure apparatus, a proximity exposure apparatus, or the like can be used. Examples of the active ray used at this time include near-infrared rays, visible rays, ultraviolet rays, and the like. Among these, ultraviolet rays are the most preferable, and low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, halogen lamps, sterilizing lamps and the like can be used as the light sources. Of these, ultra-high pressure mercury lamps are suitable. Exposure conditions vary depending on the coating thickness, but exposure is usually performed for 0.01 to 30 minutes using an ultra-high pressure mercury lamp with an output of 1 to 100 mW / cm 2.

The partition may be composed of two or more layers. By constituting the barrier ribs with two or more layers, the configuration range of the barrier rib shape can be expanded three-dimensionally. Further, in the present invention, it is preferable that the barrier rib is composed of two or more layers and the photosensitive paste of the present invention is used only for forming the uppermost layer of the barrier rib. The compound of the general formula (1) can be selectively present only at the uppermost part of the barrier wall by using the photosensitive paste of the present invention only for forming the uppermost layer of the barrier ribs by using the barrier ribs as a structure of two or more layers, It is possible to increase the tact time in the production. For example, in the case of forming a barrier rib having a two-layer structure, a first-layer photosensitive paste is applied and exposed in a stripe shape, and then a second-layer photosensitive paste is applied and exposed in a stripe shape perpendicular to the first- Development can be carried out to form barrier ribs having well sperm structures of different shapes. In addition, after the first layer is coated, the second layer is coated and then exposed in a lattice form without exposure, whereby barrier ribs of the same height as the surface of the well structure can be formed. At this time, by using a photosensitive paste that does not contain a compound having a structure represented by the general formula (1) as the first photosensitive paste and by using the photosensitive paste of the present invention as the second layer, It is possible to reduce the amount of exposure in exposure after applying the paste of the second layer as compared with the case of using a photosensitive paste and to form a partition wall having the narrowest top width.

Development is carried out by using the difference in solubility between the exposed portion and the non-exposed portion in the developing solution, but usually the immersion method, the spray method, the brush method, or the like is used. As the developing solution, an organic solvent capable of dissolving an organic component in the photosensitive paste can be used. When a compound having an acidic group such as a carboxyl group is present in the photosensitive paste, the solution can be developed with an aqueous alkali solution. As the alkali aqueous solution, sodium hydroxide, sodium carbonate, potassium hydroxide aqueous solution and the like can be used, but it is preferable to use an organic alkali aqueous solution because it is easy to remove the alkali component during firing.

As the organic alkali, general amine compounds can be used. Specifically, tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, diethanolamine and the like can be exemplified.

The concentration of the alkali aqueous solution is usually 0.05 to 5% by mass, more preferably 0.1 to 1% by mass. If the alkali concentration is too low, the soluble portion is hard to be removed. If the alkali concentration is too high, there is a risk of peeling of the pattern or corrosion of the developing apparatus, which is not preferable. It is preferable that the developing temperature at the time of development is 20 to 50 占 폚 in terms of process control.

Then, the firing is carried out at a temperature of 520 to 620 DEG C for 10 to 60 minutes in the firing furnace, and firing is performed to form barrier ribs.

Subsequently, a phosphor layer is formed by using a phosphor paste. The phosphor layer can be formed by a photolithography method using a photosensitive phosphor paste, a dispenser method, a screen printing method, or the like. The thickness of the phosphor layer is not particularly limited, but is 10 to 30 占 퐉, and more preferably 15 to 25 占 퐉. Although the phosphor powder is not particularly limited, the following phosphors are suitable from the viewpoints of light emission intensity, chromaticity, color balance, life and the like. Blue is an aluminate phosphor (for example, BaMgAl ₁₀ O ₁₇ : Eu) or CaMgSi ₂ O ₆ in which divalent europium is activated. In green, Zn ₂ SiO ₄ : Mn, YBO ₃ : Tb, BaMg ₂ Al ₁₄ O ₂₄ : Eu, Mn, BaAl ₁₂ O ₁₉ : Mn and BaMgAl ₁₄ O ₂₃ : Mn are suitable from the viewpoint of panel luminance. And more preferably Zn ₂ SiO ₄ : Mn. Similarly, (Y, Gd) BO ₃ : Eu, Y ₂ O ₃ : Eu, YPVO: Eu and YVO ₄ : Eu are preferable for red. And more preferably (Y, Gd) BO ₃ : Eu. When the phosphor is formed through the sintering step, the above-mentioned dielectric layer and the barrier rib may be fired simultaneously.

(Example)

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to this. The average particle diameter (d ₅₀ ) and the maximum particle diameter (d _max ) of the following inorganic powder were measured by Nikkiso Co., Ltd. This value is measured using the product "MT3300".

A. Photosensitive paste raw material

Ultraviolet absorber: A compound having a structure represented by the following structural formula was used.

Compound No. 1: Daiwa Kasei K.K. Product, DAINSORB T0

Compound No. 2: BASF Japan Ltd. Product, TINUVIN 329

Compound No. 3: BASF Japan Ltd. Product, TINUVIN 328

Compound No. 4: BASF Japan Ltd. Product, TINUVIN 928

Compound No. 5: BASF Japan Ltd. Product, TINUVIN P

Compound No. 6: SHIPRO Kasei Kaisha, Ltd. Product SEESORB 707

Compound No. 7: BASF Japan Ltd. Product, TINUVIN 571

In addition, the following materials were used.

Solvent:? -Butyrolactone

Photosensitive monomer 1: Trimethylolpropane triacrylate

Photosensitive monomer 2: Tetrapropylene glycol dimethacrylate

(Weight average molecular weight: 43,000, acid value: 100) added with 0.4 equivalent of glycidyl methacrylate to the carboxyl group of the copolymer composed of the photosensitive polymer: methacrylic acid / methyl methacrylate / styrene = 40/40 /

Photopolymerization initiator 1: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone (product of BASF Japan Ltd., IC369)

Photopolymerization initiator 2: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone (IC907,

Antioxidant: 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]

Organic dye: Sudan IV (manufactured by Tokyo Ohka Kogyo Co., Ltd.)

Low softening point glass powder: 7 mass% lithium oxide, 22 mass% silicon oxide, 33 mass% boron oxide, 3 mass% zinc oxide, 19 mass% aluminum oxide, 6 mass% magnesium oxide, 5 mass% Mass% (softening point: 590 캜, d ₅₀ : 2 탆, d _max : 10 탆)

High softening point glass powder: 1 mass% of sodium oxide, 40 mass% of silicon oxide, 10 mass% of boron oxide, 33 mass% of aluminum oxide, 4 mass% of zinc oxide, 9 mass% of calcium oxide, 3 mass%占 폚, d ₅₀ : 2 占 퐉, d _max : 10 占 퐉)

B. Preparation of Photosensitive Paste

The composition of the photosensitive paste is shown in Tables 1 and 2. The photosensitive paste was prepared as follows.

The organic components listed in Tables 1 and 2 were weighed and mixed and dissolved. Subsequently, the inorganic components shown in Tables 1 and 2 were added and kneaded in a three-end roller kneader to obtain a photosensitive paste. The prepared photosensitive paste was defoamed by a centrifugal deaerator.

Evaluation of compatibility and storage stability of C. paste

The compatibility of the paste was evaluated as follows. The paste immediately after the production was visually observed to confirm the presence or absence of phase separation. Further, the paste was sandwiched between two glass plates, and observed under cross-nicol using a polarizing microscope to confirm the presence of luminescent spot. When the luminescent spot is confirmed in this evaluation, it can be seen that crystals which are not commonly used in the paste exist. In the above evaluation, the case where there is no phase separation and the case where no crystal exists is rated as " o ", and the case where it is not evaluated as x.

Storage stability was evaluated as follows. The paste having the compatibility evaluation ◯ was stored in a freezer at -20 ° C. for 48 hours, taken out from the freezer, allowed to stand in the room, and then heated to room temperature. Thereafter, observation with a polarizing microscope was carried out in the same manner as in the compatibility evaluation, and the presence or absence of crystal precipitation was checked to find that the crystal was not precipitated.

D. Fabrication of bulkhead pattern

The photosensitive paste described in Tables 1 and 2 was stored in a freezer at -20 占 폚 for 48 hours, taken out from the freezer, allowed to stand in a room at 23 占 폚 and heated to room temperature to prepare a barrier rib pattern in the following order did. Asahi Glass Co., Ltd. An address electrode pattern was formed on the product "PD-200" glass substrate (42 inches) by photolithography using a photosensitive silver paste. Subsequently, a dielectric layer was formed to a thickness of 20 탆 on the glass substrate on which the address electrode was formed by screen printing. Thereafter, the photosensitive paste for forming the lower layer of the barrier rib was coated on the rear plate glass substrate having the address electrode pattern and the dielectric layer formed thereon with a slit die coater to a thickness of 100 mu m thick as a glass film having a thickness of 100 mu m, Time dried. Subsequently, the photosensitive paste for forming the upper layer of the barrier rib was applied by a slit die coater to a thickness of 20 mu m as a glass film having a thickness of 20 mu m, followed by drying at 100 DEG C for 30 minutes to obtain a photosensitive paste film having a two- . Subsequently, exposure was performed through an exposure mask. The exposure mask is a chrome mask designed to be capable of forming a stripe barrier rib pattern in a plasma display with a pitch of 160 mu m and a line width of 25 mu m. Exposure was performed by ultraviolet light exposure at an interval of 5 mJ / cm 2 from 100 mJ / cm 2 to 500 mJ / cm 2 with an ultra-high pressure mercury lamp with an output of 50 mW / cm 2 for each photosensitive paste coating film.

Subsequently, a 0.3% by mass aqueous solution of monoethanolamine kept at 35 占 폚 was developed by applying with a shower for 300 seconds, and then washed with a shower spray to remove a portion that was not photo-cured. Thereafter, the substrate was held at 560 DEG C for 30 minutes and fired to form a barrier rib.

E. Assessment of bulkhead pattern

Samples having different exposure amounts prepared by the above method were taken out to expose a cross section perpendicular to the longitudinal direction of the barrier rib, and the cross section was observed with a scanning electron microscope (Hitachi, Ltd., S2400) The width of the partition wall (bottom width) was measured. Since the width of the bottom of the barrier rib widens with the increase of the exposure amount, a sample having the bottom width of the partition wall after firing which is closest to the width of 55 mu m was selected from among the produced samples, and the width of the uppermost portion of the sample was measured. The exposure amount at which the bottom width was closest to 55 占 퐉 was defined as the optimum exposure amount. In addition, the substrate exposed at the optimum exposure amount was observed in the range of 1 cm x 1 cm from above the substrate using an optical microscope, and the presence or absence of defects at the top of the partition was confirmed. In this evaluation, it is preferable that the numerical values of the maximum width and the optimum exposure amount are both small, and that there is no defect at the top of the partition wall.

The results of the evaluation are shown in Table 1 and Table 2 as the results of evaluation of compatibility and storage stability of the paste produced. Table 3 and Table 4 show the evaluation results of the barrier rib patterns produced using these pastes.

The pastes of Examples 1 to 7 to which an ultraviolet absorber having a structure represented by the general formula (1) was added had both commercial utility and storage stability. In addition, all of the barrier rib patterns of Examples 8 to 21 produced using these pastes had a narrower top width than that of Comparative Example 8, and showed no defects at the uppermost portion of the barrier ribs. Further, since the width of the uppermost portion is narrower as the amount of the ultraviolet absorbent having the structure represented by the general formula (1) is increased, the uppermost width is controlled by adjusting the addition amount of the ultraviolet absorbent having the structure represented by the general formula (1) I can see that I can do it. In Examples 15 to 21 in which the pastes of Examples 1 to 7 were used only for forming the upper layer of the barrier ribs, the optimum width of the upper and lower layers was the same as that of Examples 8 to 14 using the pastes of Examples 1 to 7, I was able to.

On the other hand, since the paste of Comparative Example 1 did not contain an ultraviolet absorber, its compatibility and storage stability were evaluated as O, but the uppermost width of the barrier rib patterns produced using only the above paste was wider than those of Examples 8 to 21. In the pastes to which the ultraviolet absorber other than the compound having the structure represented by the general formula (1) was added, the pastes of Comparative Examples 2 to 5 had compatibility ◯, but storage stability was ×. Further, in the paste of Comparative Example 6, crystals were observed in the compatibility test, and the compatibility was evaluated as x. In addition, in Comparative Example 7, although the compound No. 7 was a liquid, it was phase-separated as droplets after the production of the paste, and the compatibility was poor. In addition, the barrier rib patterns of Comparative Examples 9 to 14 prepared using the pastes of Comparative Examples 2 to 7 contained the ultraviolet absorber crystals which were not commonly used in the paste or the defects at the uppermost part of the partition wall appearing as a space left after the droplets were removed by firing . The width of the uppermost portion of these barrier rib patterns was 34 to 38 占 퐉 and the width of the uppermost portion was wider than that of the pattern of Example 10, which was produced using a paste to which an equal amount of Compound No. 1 was added as an ultraviolet absorber.

Claims (7)

A photosensitive organic component, 2- (2,4-dihydroxyphenyl) -2H-benzotriazole, a photopolymerization initiator, and a solvent. The method according to claim 1,
Wherein the solubility parameter of the solvent is in the range of 18 to 30 MPa ^1/2 . delete The method according to claim 1,
Wherein the solvent is? -Butyrolactone. The method according to claim 1,
Wherein the photopolymerization initiator is 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone. A method for forming a pattern, comprising applying, exposing, developing, and firing the photosensitive paste according to claim 1 on a substrate. A method of manufacturing a member for a flat display panel, comprising the step of forming a barrier rib using the method for forming a pattern according to claim 6.