JP2010055921A - Method for manufacturing structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To form a pattern suitable for a flat panel display such as a PDP, an FED, and a fluorescent display tube at low cost with high accuracy. <P>SOLUTION: This method relates to manufacturing of a structure obtained by forming a structure precursor composed of a glass paste that contains an inorganic component including glass powder and an organic component on a substrate and then by firing the structure precursor. The structure precursor includes a plurality of first and second stripe-shaped structure precursors wherein two or more first and second stripe-shaped structure precursors intersect each other respectively. In the method for manufacturing the structure, when it is assumed that a height of the first structure precursors at a center position between two adjacent intersections, where the first structure precursors and the second structure precursors intersect, along the first structure precursor is h<SB>1</SB>, a height of the second structure precursors at a center position between two adjacent intersections, where the first structure precursors and the second structure precursors intersect, along the second structure precursors is h<SB>2</SB>, and a height of the first structure precursors at intersections where the first structure precursors and the second structure precursors intersect is h<SB>3</SB>, respective h<SB>1</SB>, h<SB>2</SB>and h<SB>3</SB>satisfy the following formula: h<SB>3</SB>>h<SB>1</SB>≥h<SB>2</SB>(1). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a structure, and more particularly to a method for manufacturing a structure optimal for display applications such as a plasma display panel, a field emission display, and a fluorescent display tube.

  In recent years, development of flat displays such as plasma display panels, field emission displays, fluorescent display tubes, liquid crystal display devices, electroluminescence displays, and light emitting diodes has been rapidly advanced. Among these, the plasma display generates a plasma discharge between the anode electrode and the cathode electrode facing each other in the discharge space provided between the front glass substrate and the rear glass substrate, and the gas sealed in the discharge space. Display is performed by irradiating the phosphor provided in the discharge space with the ultraviolet rays generated from the discharge. Gas discharge type displays such as plasma displays and fluorescent display tubes require partition walls for partitioning the discharge space. A field emission display such as a field emission display requires a partition for isolating the gate electrode from the cathode. In these plasma displays, field emission displays, and the like, generally, a glass paste containing glass powder or an organic component is patterned to form a partition wall precursor, and then fired to form the partition walls. In the past, stripes were mainly used for plasma display partition walls. However, in order to improve light emission efficiency, in recent years, grid-type partition walls, waffle-shaped partition walls, meanders provided with conventional stripe-shaped main partition walls and auxiliary partition walls that are substantially perpendicular thereto are used. It has been changed to a complicated shape such as a partition wall. The partition wall having these shapes has an intersection of the partition walls. At the time of firing, a large shrinkage stress is intensively generated at the intersecting portion as compared with the non-intersecting portion when the partition wall has the intersecting portion due to the volume change due to the removal of the organic component and the melting of the glass.

  As a result, the phenomenon of a recess in the intersection where the height of the partition wall is reduced only at the intersection during firing is likely to occur. If the dent of the intersection occurs, the partition of the discharge space becomes insufficient, and erroneous discharge occurs, which becomes a fatal defect as a display. Further, due to the uneven height of the partition wall, only a part of the partition wall comes into contact with the front plate, which causes a phenomenon called chipping applied by the partition wall at the contact portion. In the case of using a partition wall having a recess in the intersection, the chipping is intensively generated in the image display unit because it is in contact with the front plate at a portion other than the intersection, which is very undesirable as a display.

As a method for suppressing the intersection dent, a technique of making the intersection into a columnar shape is known (Patent Document 1). However, this method cannot completely eliminate the dents at the intersection, and has a problem that the light emitting area is reduced.
JP 2006-294501 A

  The present invention pays attention to the above-mentioned problems of the prior art, and a structure that can be freely formed at a low cost without a defect such as a dent in a cross section, such as a lattice-shaped or waffle-shaped partition wall. An object is to provide a manufacturing method.

In order to solve the above problems, the present invention has the following configuration. That is, the above-described problem is that a structure precursor composed of a glass paste containing an inorganic component containing glass powder and an organic component is formed on a substrate, and the structure precursor is fired to form a structure mainly composed of an inorganic substance. The structure precursor includes a plurality of first structure precursors in a stripe shape and a plurality of second structure precursors, and the first structure precursor Each of the bodies intersects with two or more second structure precursors, and each of the second structure precursors intersects with two or more first structure precursors, and second along the first structure precursor. The height of the first structure precursor at the center position between two adjacent intersections with the structure precursor is h ₁ , and the first structure precursor and the second structure along the second structure precursor H ₂ , the height of the second structure precursor at the center position between two adjacent intersections with the precursor, When the height of the first structure precursor at the intersection of the first structure precursor and the second structure precursor is h ₃ , h ₁ , h ₂ , and h ₃ satisfy the formula (1), respectively. This is achieved by a method for manufacturing a structure.

h ₃ > h ₁ ≧ h ₂ (1)

  According to the present invention, it is possible to form a pattern that can form a structure such as a partition optimal for a flat display such as a plasma display, a field emission display, and a fluorescent display tube at low cost with high accuracy without generating a recess in the intersection. Can provide technology.

  As a result of intensive studies on the suppression of the intersection dents, the inventors have found that this can be achieved by a method for manufacturing a structure as described below.

  That is, in the present invention, a glass paste containing glass powder and an organic component is formed into a structure precursor having a desired shape.

In the present invention, the structure precursor includes at least a plurality of stripe-shaped first structure precursors and a plurality of second structure precursors, and each of the first structure precursors includes two or more second structures. The structure precursor is crossed, and each of the second structure precursors crosses two or more first structure precursors. The structure precursor of the present invention may have a different structure in addition to the first structure precursor and the second structure precursor. In the present invention, the stripe shape means that a plurality of structures are arranged substantially in parallel. Accordingly, the shape of the structure precursor of the present invention includes structures such as a lattice pattern and a meander pattern. Furthermore, in the present invention, the height of the first structure precursor (hereinafter referred to as h ₁ ) at the center position between two adjacent intersections with the second structure precursor along the first structure precursor. , Along the second structure precursor, the height of the second structure precursor (hereinafter referred to as h ₂₎ at the center position between two adjacent intersections of the first structure precursor and the second structure precursor. And h ₁ , h ₂ , and h ₃ are respectively at the height of the first structure precursor at the intersection of the first structure precursor and the second structure precursor (hereinafter referred to as h ₃ ). It is necessary to satisfy equation (1).

h ₃ > h ₁ ≧ h ₂ (1)
As an example, FIG. 1 shows a schematic diagram of a lattice-like structure. FIG. 1A is a diagram schematically showing the shape of a structure precursor. A plurality of first structure precursors 1 in a stripe shape and a plurality of second structure precursors 2 intersecting with the first structure precursors 1 are shown. It is formed on the substrate 4. FIG. 1B is a cross-sectional view in a plane parallel to the first structure precursor 1. The height of the intersection 3 of the first structure precursor and a second structure precursor is h _3. When the distance between the centers of the intersections 3 of the first structure precursor and the second structure precursor adjacent to each other along the first structure precursor ₁ is L1, the first structure precursor and the second structure The height of the first structure precursor at a position separated by a distance ½ × L ₁ along the first structure precursor from the intersection 3 of the precursor is h ₁ . FIG. 1C is a cross-sectional view of the structure precursor in a section parallel to the second structure precursor. When the distance between the centers of the intersection 3 of the adjacent first structure precursor and the second structure precursor to L _2, the intersection 3 of the first structure precursor and a second structure precursor second structure The height of the second structure precursor at the position separated by the distance 1/2 × L ₂ along the body precursor is h ₂ .

Since h ₃ is higher than h ₁ , in the subsequent firing step, it is possible to suppress the disappearance of the organic component and the intersection dent resulting from the firing shrinkage due to the melting of the glass, and the first structure as shown in FIG. It is possible to obtain a structure in which the first structure 101 formed by firing the precursor 1 does not have a dent at the intersection 103 between the first structure and the second structure. Hereinafter, the intersection dent will be described. In the non-intersecting first structure precursor, firing shrinkage occurs only along the direction in which the first structure precursor is arranged, but the intersection of the first structure precursor and the second structure precursor. Then, since the firing shrinkage that occurs in the direction in which the first structure precursor is disposed and the firing shrinkage that occurs in the direction in which the second structure precursor is disposed act together, firing is performed in comparison with the non-intersecting portion. Later height becomes lower. This phenomenon is called intersection dent. In the present invention, the amount of the intersection dent is calculated, and the height of the intersection is formed higher than the non-intersection in advance, thereby suppressing the occurrence of the intersection dent. h ₁ and h ₃ are preferably in the relationship of the following formula.

0.02h ₁ ≦ h ₃ −h ₁ ≦ 0.3h ₁
More preferably,
0.04h ₁ ≦ h ₃ −h ₁ ≦ 0.1h ₁
It is. By setting the difference in height within this range, it is possible to suppress the depression of the intersecting portion, and the height of the intersecting portion between the first structure and the second structure after firing does not become too high. When the structure is a partition for plasma display, h ₁ is usually 100 to 250 μm, but when h ₁ is 200 μm, for example, h ₃ -h ₁ is 4 to 60 μm, more preferably 8 to 20 μm.

The height of the intersecting portion is preferably changed continuously from the non-intersecting portion connected to the intersecting portion from the viewpoint of alleviating the firing shrinkage. L ₁ is usually 150 to 3000 μm, but the length (La) for continuously changing the height is preferably 1/3 or less of L ₁ and more preferably 1/4 or less. Furthermore, by making La larger than h ₃ -h ₁ , the inclination in the height direction of the structure precursor intersection and the non-intersection is made gentle, and the mold release property at the time of molding is improved and cracks are caused by firing shrinkage. And disconnection can be suppressed. In view of the above, La is preferably in the range of the following formula.

(H ₃ −h ₁ ) ≦ La ≦ 0.33L ₁
More preferably,
2 (h ₃ −h ₁ ) ≦ La ≦ 0.25L ₁
By making the length (La) that continuously changes the height within this range, defects such as cracks and disconnection due to firing shrinkage are suppressed, and depressions at the intersection are sufficiently suppressed, and the height becomes too high. Nor.
The molding method for molding the glass paste into the shape of the structure precursor is not particularly limited, such as a photosensitive paste method, a lift-off method, a sand blast method, a chemical etching method, and a mold transfer method. For example, in the photosensitive paste method, the sand blast method, and the chemical etching method, the height of the structure precursor can be changed by controlling the coating film thickness by repeating a plurality of coatings. On the other hand, the mold transfer method is preferable from the viewpoint that it is easier to freely change the height of the structure precursor. Here, the mold transfer method is mainly a step of preparing a mold having a recess corresponding to a structure pattern, and a step of filling the glass paste between the recess of the mold and the substrate, and then transferring the glass paste to the structure precursor. It refers to the method of forming into. In order to partially change the height of the structure precursor as in the present invention, it is only necessary to partially increase the depth of the concave portion of the corresponding mold.

  Mold materials include nickel-chromium alloy, nickel-molybdenum alloy, alloy steel such as nickel and chromium-molybdenum alloy, inorganic materials such as stainless steel, silicon and quartz, acrylic resin, silicone resin, urethane resin, epoxy resin Organic materials such as fluororesin are used. An organic material is preferable in order to reduce the manufacturing cost of the mold.

  Two examples of a method for producing a mold using an organic material will be described, but the present invention is not limited thereto.

  The first example is a method using a matrix having a recess corresponding to the shape of the target structure. The mother mold can be manufactured by cutting an alloy such as steel, carbon steel, aluminum alloy, stainless steel, copper alloy, titanium alloy, or an inorganic material such as glass with a diamond tool. The matrix has a recess corresponding to the shape of the target structure, and can be designed in consideration of the shrinkage rate due to the curing of the organic material and the shrinkage rate due to the curing and firing of the glass paste. In the present invention, in the matrix, the depth of the groove corresponding to the first structure precursor is deeper at the portion corresponding to the intersection with the second pattern. By setting the depth of the matrix in this way, it is possible to control the height of the structure precursor and suppress the dent at the intersection due to firing shrinkage. The mother mold may be used as it is, but is preferably used after being subjected to a mold release treatment with a mold release agent or the like.

  The second example is a method for manufacturing a matrix having the same shape as the target structure. For example, by forming a photosensitive paste coating film, performing pattern exposure through an exposure mask having a pattern, providing a contrast to the developer, and removing only the developer soluble portion by development, A matrix having the same shape as the structure to be manufactured is manufactured. In this photosensitive paste method, various methods have been proposed as a method for forming a partition wall of a display member, and any method can be used for forming the matrix of the present invention. For example, a negative type containing a photocurable compound and accelerating the photocuring reaction at the exposed portion to give contrast to the developer can also be used. In this case, for example, by repeating application and exposure several times, it becomes possible to continuously change the height of the matrix. It is also preferable to use a positive photosensitive paste that exhibits alkali solubility by exposure. When the positive type photosensitive paste is used, the height of the mother die can be controlled by the exposure amount, so that it is possible to obtain mother die having different heights continuously by one application / development / development. When glass paste is used as the photosensitive paste, it is also preferable to obtain a matrix made of substantially only inorganic components by baking the pattern. As described above, using a matrix made of only an inorganic substance improves the releasability and easily avoids defects. For the purpose of improving the releasability, it is also preferable to use after being subjected to a release treatment with a release agent.

  Subsequently, a mold material is applied to the above-described mother mold. As the mold material, as described above, an organic material such as an acrylic resin, a silicone resin, a urethane resin, and an epoxy resin can be used. From the viewpoint of releasability and transparency, an acrylic resin, a silicone resin, A urethane resin is preferably used.

  As the acrylic resin, an acrylic resin composition containing an additive such as a (meth) acrylic monomer, a polymerization initiator, a binder resin, a solvent, a plasticizer or a surfactant is preferably used. For the purpose of improving flexibility, it is also preferable to add a urethane compound.

  As the silicone resin, those which can be cured at a low temperature are preferable. It is preferable to cure at room temperature to 150 ° C., more preferably at room temperature to 100 ° C., for 0.1 minute to 48 hours. By setting the curing temperature and the curing time within these ranges, occurrence of dimensional deviation due to heat can be suppressed. Examples of the thermosetting silicone resin include Sylpot 184 (manufactured by Toray Dow Corning) and SH9555 (manufactured by Toray Dow Corning). It is also preferable to use an ultraviolet (UV) curable silicone resin. Since the UV curable silicone resin can be cured by UV irradiation, it can be cured in a short time without dimensional change. Examples of the UV curable silicone resin include KER-4000UV and KER-4100UV (manufactured by Shin-Etsu Silicone).

  Examples of the method for applying the mold material include, but are not limited to, laminating, screen printing, knife coater, bar coater, roll coater, spin coater, die coater, and blade coater. Lamination application is a method in which a molding material is uniformly laminated between a support film and a mother die. When other coating methods are used, the support film is placed on the molding material coating film after the molding material is applied. Be careful not to get any air bubbles when applying. In order to prevent bubbles from being mixed, it is also preferable that the pressure is reduced during or after application. The support film preferably has good dimensional stability. Further, when UV irradiation is used in the subsequent mold material curing step, the support film preferably transmits UV. Specifically, a transparent film such as PET, PPS, or polypropylene is preferably used. After disposing the support film, the film thickness can be made uniform with a press device, a vacuum press device, a laminating device, or the like, if necessary. Subsequently, the mold material is cured using a method according to the properties of the mold material, such as heat curing, room temperature curing, and UV curing, and peeled from the mother mold to obtain a mold. Although the mold may be used as it is, it is preferably used after being subjected to a release treatment with a release agent or the like.

  When the obtained mold has the same unevenness as the desired partition wall, the mold is further transferred and produced. Although the manufacturing method may be the same as the above-described manufacturing method of the mold, it is preferable to use a different material for the mold material from the viewpoint of improving the releasability. In this way, a mold having irregularities opposite to the desired partition walls is obtained.

  Subsequently, a process of filling a glass paste between the concave portion of the mold and the substrate will be described.

  First, prepare a glass paste. The glass paste needs to contain an inorganic component and an organic component including glass powder. Although it does not specifically limit as glass powder, It is preferable to contain low softening point glass. In the present invention, the low softening point glass powder refers to a glass powder having a load softening temperature in the range of 400 to 600 ° C. This is because when the load softening temperature is within this range, there is no deformation of the structure during sintering and the meltability becomes appropriate. A more preferable range of the load softening temperature is 400 to 550 ° C. The proportion of the low softening point glass powder in the inorganic component is preferably 60% by volume to 100% by volume. By setting the content ratio within this range, sintering during firing can be made sufficient, and the porosity of the structure after firing can be suppressed to an appropriate range.

  The particle diameter of the glass powder is selected in consideration of the shape of the structure to be produced. The 50% particle diameter (average particle diameter) in the weight distribution curve is 0.1 to 3.0 μm, and the maximum particle diameter (top Size) is preferably 20 μm or less.

  When using photocuring for hardening of glass paste, it is preferable that the refractive index of glass powder is 1.50-1.70. Photocuring is facilitated by matching the refractive indexes of the glass powder and the organic component and suppressing light scattering.

  The glass powder that can be preferably used has, for example, the following composition in oxide notation.

Lithium oxide, sodium oxide or potassium oxide 3-15% by mass
Silicon oxide 5-30% by mass
Boron oxide 20-45 mass%
Barium oxide or strontium oxide 2-15% by mass
Aluminum oxide 10-25% by mass
Magnesium oxide or calcium oxide 2-15% by mass
As described above, at least one kind of alkali metal oxides of lithium oxide, sodium oxide, or potassium oxide is used, and the total amount is preferably 3 to 15% by mass, and more preferably 3 to 10% by mass.

  Further, although not described in the above composition, it is also preferable to contain zinc oxide, titanium oxide, zirconium oxide or the like.

  The glass paste in the present invention preferably contains a filler component as an inorganic component. The filler component here is added to improve the strength, reflectance, and firing shrinkage of the structure, and refers to inorganic fine particles that hardly melt and flow even at the firing temperature. Specifically, it refers to an inorganic fine particle that does not have a softening temperature, a melting point, or a decomposition temperature at 600 ° C. or less and exists as a solid at 600 ° C. By adding the filler component, it is possible to suppress the shrinkage due to the firing of the pattern and improve the strength of the pattern. Moreover, the reflectance of the structure after baking can also be improved by adding photorefractive index components, such as a titania and an alumina.

  In the present invention, the filler component includes silica-based composite oxide particles, ceramic powder such as high softening point glass powder having a load softening temperature of 600 to 1200 ° C., cordierite, titania, alumina, silica, magnesia, zirconia, and the like. At least one selected can be preferably used.

  A filler component having an average particle diameter of 0.01 to 3.0 μm can be preferably used in consideration of dispersibility and filling properties in the glass paste.

  As an organic component in the glass paste used for this invention, it is preferable to contain a sclerosing | hardenable compound, a polymerization initiator, etc.

  By containing the curable compound, the glass paste can be cured by light or heat after filling into the mold, and the pattern retention and the mold releasability from the mold can be improved. The curable compound is not particularly limited as long as it is cured by energy such as light and heat, but is preferably a photocurable compound, and particularly preferably a (meth) acrylic monomer. By using a photocurable compound such as a (meth) acrylic monomer, it can be cured by exposure, and a high-aspect ratio, high-definition structure can be formed with high accuracy.

  Examples of (meth) acrylic monomers include (meth) acrylic acid esters and carboxylic acids (for example, methanol, ethanol, propanol, hexanol, octanol, cyclohexanol, glycerin, trimethylolpropane, pentaerythritol, etc.). Propionic acid, benzoic acid, acrylic acid, methacrylic acid, succinic acid, maleic acid, phthalic acid, tartaric acid, citric acid, etc.) and glycidyl (meth) acrylate, amide derivatives (eg acrylamide, methacrylamide) N-methylolacrylamide, methylenebisacrylamide, etc.), a reaction product of an epoxy compound and (meth) acrylic acid, etc., but it is preferable to use a polyfunctional compound having two or more functional groups at least in part. . By using a polyfunctional compound, the glass paste used in the present invention can be efficiently crosslinked. Examples of such polyfunctional compounds include butanediol diacrylate, hexanediol diacrylate, nonanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, and polyethylene glycol diacrylate. , Propylene glycol diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polytetramethylene glycol diacrylate, neopentyl glycol diacrylate, glycerin diacrylate, 2-hydroxy-3-acryloyloxypropyl acrylate, dimethylol-tricyclo Decane diacrylate, bisphenol A diacrylate, ethylene Side-modified bisphenol A- diacrylate, propylene oxide-modified bisphenol A- diacrylate. Examples of trifunctional or higher polyfunctional compounds include trimethylolpropane triacrylate, ethylene oxide modified trimethylolpropane triacrylate, propylene oxide modified trimethylolpropane triacrylate (above trifunctional compound), pentaerythritol tetraacrylate, ditrimethylol. Examples include propanetetraacrylate, (tetrafunctional compound), dipentaerythritol hexaacrylate (hexafunctional compound), and the like. In these polyfunctional compounds, some or all of the acrylic groups may be replaced with methacrylic groups. In the present invention, one or more of these can be used.

  The curable compound is preferably 0.1 to 60% by weight in the glass paste. More preferably, it is 3 to 30% by weight. By setting the content within this range, it is possible to improve pattern retention and mold release from the mold, and to suppress shrinkage during curing and firing.

  Furthermore, it is preferable to contain a polymerization initiator. By adding a polymerization initiator, the glass paste can be cured more smoothly by light or heat.

  The polymerization initiator (B) used in the present invention is preferably one that generates radical species by light irradiation or heat. As the polymerization initiator, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1 -One, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) ) Oxime, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, benzoin , Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Ter, benzoin isobutyl ether, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, alkylated benzophenone, 3,3 ' , 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-Benzoylbenzyl) trimethylammonium chloride, 2-hydroxy-3- (4-benzoylphenoxy) -N, N, N-trimethyl-1-propenaminium chloride monohydrate, 2-isopropylthioxanthone, 2,4- Dimethylthio Xanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2-hydroxy-3- (3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl- 1-propanaminium chloride, 2,4,6-trimethylbenzoylphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2-bi Imidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methylphenylglyoxyester, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-Hexafluorophosphate (1-), diphenyl sulfide derivative, bis η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 4,4-bis (dimethylamino) benzophenone, 4 , 4-bis (diethylamino) benzophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 4-benzoyl-4-methylphenylketone, dibenzylketone, fluorenone, 2,3-diethoxyacetophenone, 2,2-dimethoxy 2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, benzylmethoxyethyl acetal, anthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, β- Chloranthraki , Anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2, -Phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, N-phenylglycine, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile, benzthiazole disulfide, triphenylphosphine, carbon tetrabromide, tribromophenylsulfone, benzoyl peroxide and eosin, methylenebutene Examples include a combination of a photoreductive dye such as roux and a reducing agent such as ascorbic acid or triethanolamine.

  In the present invention, one or more of these can be used. The polymerization initiator is preferably contained in the glass paste in the range of 0.005 to 10% by weight, and more preferably 0.01 to 5% by weight. By setting the content of the polymerization initiator within this range, the glass paste can be cured smoothly.

  The glass paste used in the present invention preferably contains a plasticizer. By containing a plasticizer, the viscosity of the glass paste can be reduced, and the filling property into the mold can be improved. Further, it is possible to obtain an effect of reducing the curing shrinkage at the time of curing and greatly suppressing defects such as deformation and cracking of the structure due to the curing shrinkage. Plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dinonyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, dioctyl adipate, etc. , Adipates such as dinonyl adipate and di-2-butoxyethyl adipate, azelaates such as dioctyl azelate, sepacate, tricresyl phosphate, tributyl acetylcitrate, epoxidized soybean oil, trimellitic ester Among them, a plasticizer containing one or more of these may be mentioned, and from the viewpoint of safety, adipic acid esters, sepacic acid esters and the like are particularly preferable. The plasticizer content in the glass paste is preferably 0.1 to 50% by weight, more preferably 0.5 to 30% by weight.

  The glass paste used in the present invention preferably contains a urethane compound. By containing the urethane compound, the firing stress can be reduced in the subsequent firing step, and the effect of the recess in the intersection can be made sufficient, and there is also an effect of suppressing defects such as disconnection and cracking.

  The urethane compound preferably has a weight average molecular weight of 15,000 to 100,000. By setting the weight average molecular weight within this range, the flexibility and toughness of the mold can be made sufficient, and the compatibility of the curable resin composition for molds can be maintained. More preferably, it is 18000-80000.

Furthermore, the urethane compound is preferably represented by the following general formula (3).
R _< ¹ _> -(R _< ² _> -R _< ³ _> ) _n- R _< ⁴ _> -R _< ⁵ _> (3)
(Here, R ¹ and R ⁵ are each selected from an organic group containing an ethylenically unsaturated group, hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and a hydroxyalkyl group. R ² and R ⁴ are each an organic group containing a urethane bond, R ³ is an alkylene oxide chain, and n is a natural number of 1 to 10.
In General Formula (3), R ¹ and R ⁵ were selected from any of a substituent containing an ethylenically unsaturated group, hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and a hydroxyalkyl group. However, it is preferable that at least one of them is a substituent containing an ethylenically unsaturated group, and it is more preferable that both R ¹ and R ⁵ are substituents containing an ethylenically unsaturated group. By containing an ethylenically unsaturated group, the above-mentioned curable compound and a crosslinked structure are formed, and the effect of improving toughness and suppressing microlayer separation is also obtained. It is particularly preferable that the substituent containing an ethylenically unsaturated group is a (meth) acryl group.

R ³ is an alkylene oxide chain, but the molding compound can be made more flexible when the urethane compound contains an alkylene oxide chain. Further, the compatibility of the glass paste can be easily improved by controlling the polarity of the alkylene oxide chain. Specific examples of the urethane compound preferably used in the present invention include UA-340P (molecular weight 42000), UA-340PM (molecular weight 42000), UA-2235PE (molecular weight 18000), UA-3238PE (molecular weight 19000), UA-3348PE ( Molecular weight 22000), UA-5348PE (molecular weight 39000) (above, manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like, but are not limited thereto. Moreover, you may use these compounds in mixture.

  The urethane compound is preferably contained in the glass paste in an amount of 1 to 40% by weight. More preferably, it is 1 to 25% by weight. By making content into this range, the effect of a urethane compound can be made sufficient.

  The glass paste used in the present invention can also contain a surfactant. By containing a surfactant, the surface tension of the glass paste can be reduced to improve the releasability, so that defects such as plastic deformation, peeling, cracks, etc. occur when the structure pattern is released from the mold. Can be suppressed.

  The surfactant is preferably a fluorine atom-containing surfactant. By using a fluorine atom-containing surfactant, the effect of reducing the surface tension of the glass paste can be greatly increased, and defects such as plastic deformation, peeling, and cracking can occur when the partition pattern is released from the mold. Can be suppressed.

  The glass paste used in the present invention may contain a binder resin. The binder resin preferably has a function as a binder for satisfactorily dispersing inorganic fine particles such as glass powder and filler during pattern formation, and is decomposed and removed during firing. Examples of binder resins that are preferably used include, but are not limited to, acrylic resins, cellulosic resins, epoxy resins, melamine resins, phenol resins, urea resins, vinyl chloride resins, polyethylene, and polypropylene. . An acrylic resin is particularly preferable from the viewpoints of compatibility and easy decomposability. It is preferable that the glass transition point (henceforth Tg) of an acrylic resin is -50-50 degreeC, More preferably, it is 0-25 degreeC. By setting the Tg of the acrylic resin within this range, it becomes possible to achieve both ease of handling and flexibility.

  The glass paste used for this invention can contain a solvent further as needed. As the solvent, commonly used solvents can be used. For example, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, benzyl alcohol, 3 -Methoxy-3-methyl-1-butanol, 2,2,2-trimethyl-1,3-pentanediol monoisobutyrate, terpineol, butyl carbitol, butyl carbitol acetate, tetrahydrofuran, dimethyl sulfoxide, γ- Butyrolactone, bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, etc. and organic solvent mixtures containing one or more of these are used. .

  Subsequently, a process of filling a glass paste between the concave portion of the mold and the substrate will be described. Examples of the method for filling the glass paste include a method in which the glass paste is first applied to the substrate and the mold is pressure-bonded, and a method in which the glass paste is filled in the mold and is crimped to the substrate. A method for applying the glass paste and crimping the mold will be described in detail below.

  As a method for applying the glass paste, methods such as screen printing, knife coater, bar coater, roll coater, die coater, and blade coater can be used, and drying can be performed as necessary. The coating thickness can be determined in consideration of the volume of the desired structure pattern and the shrinkage rate due to drying, curing and firing of the glass paste. Usually, it is in the range of 80 to 500 μm. The coating thickness can be adjusted by coating conditions, the viscosity of the curable resin composition, and the like.

  Next, a forming die is pressure-bonded onto the substrate coated with the glass paste. The pressure-bonding method is not particularly limited, but if a lamination method using a vacuum press or a laminate roll is used, a uniform film free from voids and bubbles can be obtained.

The glass paste is cured in a state where the mold and the glass paste are pressure-bonded to the substrate. Examples of the curing method include thermal curing and actinic light irradiation. In the present invention, the glass paste is preferably made photocurable. Examples of the active light source used at this time include near ultraviolet rays, ultraviolet rays, electron beams, X-rays, and laser beams. Among these, ultraviolet rays are most preferable, and as the light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a halogen lamp, or a germicidal lamp can be used. The light irradiation conditions vary depending on the coating thickness, but are usually performed for 0.01 to 10 minutes using an ultrahigh pressure mercury lamp with an output of 1 to 100 mW / cm ² .

Then, a board | substrate and glass paste are isolate | separated from a shaping | molding die, and a structure precursor is obtained. The obtained structure precursor has a height h ₁ of the first structure precursor at the center position between two adjacent intersections with the second structure precursor along the first structure precursor. The height of the second structure precursor h ₂ at the center position between two adjacent intersections of the first structure precursor and the second structure precursor along the two structure precursors h ₂ , the first structure When the height of the first structure precursor at the intersection of the precursor and the second structure precursor is h ₃ , h ₁ , h ₂ , and h ₃ must satisfy Formula (1), respectively. is there.

h ₃ > h ₁ ≧ h ₂ (1)
Subsequently, the molded structure precursor is fired to form a structure that is substantially made only of an inorganic substance. The firing atmosphere and temperature vary depending on the type of glass paste and substrate, but firing is performed in an atmosphere of air, nitrogen, hydrogen, or the like. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used, and firing is performed at a temperature of 350 to 800 ° C., preferably 480 to 620 ° C. for 1 to 60 minutes. Can do. By setting the firing temperature and firing time within these ranges, the organic components can be sufficiently removed to melt the glass, the power during firing can be suppressed, and the distortion of the substrate can be suppressed. In the obtained structure, the height of the first structure at the center position between two adjacent intersections with the second structure along the first structure is H ₁ , and the first along the second structure. The height of the second structure at the center position between two adjacent intersections between the structure and the second structure is H ₂ , and the height of the first structure at the intersection between the first structure and the second structure When the thickness is H ₃ , it is preferable that H ₁ and H ₃ each satisfy the formula (2).

0 μm ≦ | H ₃ −H ₁ | ≦ 10 μm (2)
Furthermore, although the method of forming the partition for plasma displays which consists of a main partition and an auxiliary partition by this invention is demonstrated, this invention is not limited to this. As the partition for plasma display, for example, the main partition has a width of 10 to 100 μm, a height of 80 to 250 μm, and a pitch of 50 to 1000 μm, and the auxiliary partition has a width of 10 to 1000 μm, a height of 20 to 250 μm, and a pitch of 150 to 3000 μm. Such a lattice-shaped partition wall is mentioned.

  First, a mold is prepared. The mold may have irregularities opposite to the desired partition wall shape, and the depth of the portion corresponding to the intersection of the main partition wall and the auxiliary partition wall may be deeper than the other part of the main partition wall, but is transparent. It is preferable.

Subsequently, a glass paste is prepared. The glass paste is not particularly limited, but a material that can be filled in a mold and can hold a pattern after mold release is preferably used. A material that is cured by reaction with light or heat is more preferable, and in the case of forming a partition with high accuracy and a high aspect ratio, it is particularly preferable to use a photosensitive composition that is cured by light. When the mold produced according to the present invention is transparent, a highly accurate and high aspect ratio pattern can be quickly formed with a small exposure by using the photosensitive composition. In order to provide photosensitivity, it is achieved by containing a curable compound and a photopolymerization initiator. An example of the glass paste is shown below.
Curing compound: polyethylene glycol diacrylate (3 to 20% by weight)
Polymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (0.05 to 10% by weight)
・ Solvent: Kyowanol M (0-30% by weight)
Inorganic particles: A mixture of low softening point glass and ceramic filler (40 to 97% by weight)
Subsequently, a glass paste is applied to the substrate. As a coating method, it can apply | coat using methods, such as screen printing, a bar coater, a roll coater, a die coater, a blade coater, and can be dried as needed. The coating thickness can be determined in consideration of the desired height of the partition wall precursor and the shrinkage rate of the glass paste. The coating thickness can be adjusted by the number of coatings, the screen mesh, the viscosity of the glass paste, and the like. Drying is performed using a hot air dryer, IR dryer, or the like, and the drying temperature and time can be adjusted by the solvent and coating film thickness of the glass paste used.

  Next, the mold of the present invention is pressure-bonded onto the glass paste coating film. The pressure-bonding method is not particularly limited, but when a laminating method using a laminating roll is used, a uniform film free from voids and bubbles can be obtained.

In the case of using a photocurable glass paste, light irradiation can be performed in a state where the mold is pressed against the glass paste. Examples of the active light source used at this time include near ultraviolet rays, ultraviolet rays, electron beams, X-rays, and laser beams. Among these, ultraviolet rays are most preferable, and as the light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a halogen lamp, or a germicidal lamp can be used. Although light irradiation conditions differ with application | coating thickness, it is normally performed for 0.01 to 30 minutes using the ultrahigh pressure mercury lamp of the output of 1-100 mW / cm < ² >.

  Thereafter, the mold is removed from the glass paste coating film to obtain a desired partition wall. The obtained partition walls are free from defects such as deformation, cracks, and disconnection. When firing in a later step, the mold can be removed by firing.

  Subsequently, firing is performed in a firing furnace. The firing atmosphere and temperature vary depending on the type of glass paste and substrate, but firing is performed in an atmosphere of air, nitrogen, hydrogen, or the like. As the firing furnace, a batch-type firing furnace, a belt-type continuous firing furnace, or the like can be used, and firing is performed at a temperature of 350 to 800 ° C., preferably 520 to 620 ° C. for 1 to 60 minutes. Further, as described above, firing can be performed without separating the mold from the glass paste. In the case where the mold is composed only of organic components, the mold can be removed from the molding material by firing.

  FIG. 2 schematically shows an example of a method for forming the partition walls of the plasma display using the above-described partition wall forming mold and photocurable glass paste.

  First, as shown in FIG. 2A, a substrate 10 provided with a stripe-shaped address electrode 8 and a dielectric layer 9 covering the address electrode 8 on a glass substrate 7 is prepared. Glass paste 11a is applied. Next, the glass mold 11 a is filled between the substrate 10 and the molding die 5 by placing the molding die 5 described above and press-bonding using the laminate roll 6.

  Next, as shown in FIG. 2 (b), the glass paste 11a is cured by irradiating the ultraviolet rays 12 from the mold 5 side, and then the mold 5 is peeled off from the substrate 10 and the cured glass paste, and FIG. The substrate 10 having the partition wall pattern 11b as shown in FIG. Furthermore, by firing this, a member for plasma display having the partition walls 11c can be obtained.

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to this. Using the present invention, a 42-inch plasma display having 2.70 million pixels (1920 pixels × 1080 pixels) was manufactured.

A. Preparation of Mold A mold was prepared by curing a silicone resin composition (Sylpot 184, manufactured by Toray Dow Corning Co., Ltd.). The produced mold corresponds to a groove corresponding to a main partition wall precursor having a top line width (opening width) of 70 μm and a bottom line width of 40 μm, and an auxiliary partition wall precursor having a top line width (opening width) of 80 μm and a bottom line width of 40 μm. a groove, when the height _h 1 of the partition wall _precursor, h 2, the groove corresponding to _{h 3} depth and _{d 1,} d 2, _{d 3 respectively,} d _1, d 2, _{d 3} Table It was as 1. The pitch of the grooves corresponding to the main partition wall precursor was 160 μm, and the pitch of the grooves corresponding to the auxiliary partition wall precursor was 480 μm. The length (La ₀ ) for continuously changing the depth of the groove corresponding to the main partition wall precursor was as shown in Table 1.

B. Method for Producing Plasma Display Partition Wall Using the prepared mold, a plasma display partition wall was produced by the following procedure. An address electrode pattern having a pitch of 160 μm and a line width of 50 μm was formed on a “PD-200” glass substrate (42 inches) manufactured by Asahi Glass Co., Ltd. by photolithography using a photosensitive silver paste. Next, a dielectric layer having a thickness of 16 μm was formed on the glass substrate on which the address electrodes were formed by screen printing. Thereafter, a glass paste having the composition shown below was uniformly applied on the back plate glass substrate on which the address electrode pattern and the dielectric layer were formed by a die coating method so as to have a thickness of 100 μm.
(Composition of glass paste)
Curing compound: EO-modified bisphenol A diacrylate (manufactured by NOF Corporation) 10% by weight
-Urethane compound: UA-340P (molecular weight 43000, manufactured by Shin-Nakamura Chemical Co., Ltd.) 1.5% by weight
・ Polymerization initiator: bis (2,4,6-trimethylbenzoy) -phenylphosphine oxide (Ciba Specialty Chemicals) 0.2% by weight
・ Dispersant: Nonyl ether dispersant 1.5% by weight
Plasticizer: 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate 16.8% by weight
Inorganic particles: 70% by weight of a mixture of low softening point glass (overweight softening point 510 ° C.) and ceramic filler
Then, the above-mentioned shaping | molding die was crimped | bonded to the glass paste by the laminating method by a laminating roll. The glass substrate, the dielectric layer, and the electrode were used, and the substrate was exposed to ultraviolet rays for 20 seconds with an ultrahigh pressure mercury lamp with an output of 50 mW / cm ² from the mold surface while the support was pressed against the substrate. Thereafter, the mold was peeled off from the partition glass paste to obtain a partition wall precursor having a desired partition shape. The obtained partition walls were observed for size, cracks, disconnections, and height irregularities. Of the heights of the partition wall precursors, h ₁ , h ₂ , h ₃ , and the length La that continuously changes the height are as shown in Table 1, respectively. Moreover, the pitch of the main partition wall precursor was 160 μm, and the pitch (L ₁ ) of the auxiliary partition wall precursor was 480 μm.

Then, the partition was formed by hold | maintaining for 30 minutes and baking at 550 degreeC. Among the heights of the partition walls, H ₁ , H ₂ , and H ₃ are as shown in Table 1. If the amount of height unevenness (| H ₁ −H ₃ |) at the intersection is 4 μm or less, the height unevenness evaluation is AA, if 4 μm <| H ₁ −H ₃ | ≦ 5 μm, the height unevenness evaluation is A, 5 μm <| H _{If 1} −H ₃ | <10 μm, the height unevenness evaluation is B, and if it is 10 μm or more, the partition is not possible, and the height unevenness evaluation is C. Defect assessment is AA if cracks and breaks are within 1 location, A is defect assessment if within 2-5 locations, B is defect assessment if within 6-20 locations, and it is not possible as a partition with more than 20 locations. The defect evaluation was C.

C. Method for Producing Plasma Display A phosphor layer was formed to a thickness of 20 μm on the obtained substrate with barrier ribs by a dispenser method and baked to obtain a plasma display back plate.

  Subsequently, a plasma display front plate was produced by the following procedure. An ITO electrode having a thickness of 1 μm was formed on a “PD-200” glass substrate (42 inches) manufactured by Asahi Glass Co., Ltd. by a photoetching method, and then a bus electrode pattern was formed by a photolithography method using a photosensitive silver paste. . Thereafter, a transparent dielectric layer was formed to a thickness of 30 μm by screen printing. Finally, a 500 nm thick MgO film was formed by electron beam evaporation to obtain a front plate.

  After sealing the produced front plate and back plate, a noble gas of xenon-neon mixed gas of 5% by volume of xenon is sealed in a space formed between the front and back substrates at a pressure of 450 mmHg, thereby plasma display A panel portion was prepared. In addition, a plasma display having 2.70 million pixels was fabricated by mounting a driver IC for driving. The obtained plasma display was turned on every other row along the partition wall direction, and was visually evaluated for lighting, non-lighting, or flickering due to erroneous discharge. The evaluation is AA if the number of lit cells or non-lighted cells due to erroneous discharge is within one, the display evaluation is A if it is within 2 to 5, and the display evaluation is B if it is within 6 to 20. 20 or more is not possible as a display panel, and C. When only flickering occurred, the display evaluation was A.

Example 1
The partition for plasma display produced using the mold shown in Table 1 has no intersection dents, has a good shape and no defects, and has a height unevenness evaluation and defect evaluation of AA. When the display was produced, display evaluation was also AA.

(Example 2)
The d ₃ to 185μm from 180 [mu] m, in addition to changing the La from 50μm to 100μm Example 1 was repeated,. The obtained partition for plasma display had no intersection dents, had a good shape and no defects, height unevenness evaluation and defect evaluation were AA, and when a plasma display was produced, display evaluation was also AA. .

(Example 3)
Example 1 was repeated except that d ₃ was changed from 180 μm to 175 μm and La was changed from 50 μm to 65 μm. The obtained partition for plasma display had no intersection dents, had a good shape and no defects, height unevenness evaluation and defect evaluation were AA, and when a plasma display was produced, display evaluation was also AA. .

Example 4
Example 1 was repeated except that no urethane compound was added. The obtained partition wall for plasma display had a slightly large intersection dent amount of 5 μm, and the height unevenness evaluation was A. Three disconnections occurred, and the defect evaluation was A. This is probably because the stress during firing was increased because the urethane compound was not added. When the plasma display was produced, the display evaluation was also B.

(Example 5)
Example 1 was repeated except that La was 5 μm. The obtained plasma display partition walls had a small recess at the intersection, but 12 cracks occurred along the intersection, and the defect evaluation was B. When the plasma display was produced, the display evaluation was also B.
(Example 6)
Example 1 was repeated except that d ₁ , d ₂ , d ₃ , and La of the mold were changed. The obtained partition for plasma display had no intersection dents, had a good shape and no defects, height unevenness evaluation and defect evaluation were AA, and when a plasma display was produced, display evaluation was also AA. .
(Example 7)
Another of changing the d ₃ from 180μm to 202μm Example 1 was repeated,. The obtained partition wall for plasma display was 8 μm higher at the intersection, and the height unevenness evaluation was B. Furthermore, eight cracks occurred along the intersection, and the defect evaluation was B. When the plasma display was produced, the display evaluation was also B.
(Example 8)
Another of changing the d ₃ from 180μm to 173μm Example 1 was repeated,. The obtained partition for plasma display had a crossing portion 7 μm lower, and the height unevenness evaluation was B. When the plasma display was produced, the display evaluation was also B.
(Comparative Example 1)
Another of changing the d ₃ from 180μm to 170μm Example 1 was repeated,. The obtained partition for plasma display had an intersection of 11 μm higher, and the height unevenness evaluation was C. When the plasma display was produced, the display evaluation was also C.

It is the figure which showed typically the shape of this invention structure precursor and the structure. It is the figure which showed typically an example of the method of forming the partition of a plasma display by this invention.

Explanation of symbols

1: first structure precursor 2: second structure precursor 3: intersection of first structure precursor and second structure precursor 101: first structure 102: second structure 4: substrate 5 : Mold 5: Glass substrate 6: Laminate roll 7: Glass substrate 8: Address electrode 9: Dielectric layer 10: Substrate 11a: Glass paste 11b: Partition precursor 11c: Partition 12: Ultraviolet

Claims (3)

A structure in which a structure precursor composed of an inorganic component containing glass powder and a glass paste containing an organic component is formed on a substrate, and the structure precursor is fired to form a structure mainly composed of an inorganic substance. The structure precursor includes a plurality of striped first structure precursors and a plurality of second structure precursors, and each of the first structure precursors is two or more. Each of the second structure precursors, and each of the second structure precursors intersects with two or more first structure precursors, and the second structure precursors extend along the first structure precursors. The height of the first structure precursor at the center position between two adjacent intersections of h ₁ is h ₁ , and the first structure precursor and the second structure precursor are adjacent to each other along the second structure precursor. The height of the second structure precursor at the center position between the two intersections is h ₂ , and the height of the first structure precursor and the first structure precursor When the height of the first structure precursor at the intersection with the two structure precursors is h ₃ , h ₁ , h ₂ , and h ₃ each satisfy the formula (1). Production method.
h ₃ > h ₁ ≧ h ₂ (1) The step of forming a structure precursor made of the glass paste includes a step of preparing a mold having a recess corresponding to the structure precursor, a step of filling the glass paste between the recess of the mold and the substrate, The method of manufacturing a structure according to claim 1, further comprising a step of transferring the filled glass paste onto a glass substrate. The method for manufacturing a display member, wherein the structure is a partition wall of a display member, and the structure precursor is a partition wall precursor, and the partition wall is formed by the structure manufacturing method according to claim 1.

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