JP2007246568A - Resin composition containing inorganic particle, transfer film and method for producing member for displaying panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inorganic particle-containing organic resin composition capable of forming a member having an excellent pattern form and a high aspect ratio, excellent in burning property of the organic component in baking process and capable of producing a highly reliable display panel, a transfer film formed by the composition and a method for producing a member for a display panel. <P>SOLUTION: This inorganic particle-containing resin composition is provided by containing oxide fine particles having 0.001 to 5 μm range mean particle diameter, 1.4 to 1.8 range refractive index and 0.5 to 300 m<SP>2</SP>/g range specific surface area, glass powder, an alkali soluble resin and a radiation sensitive component, and the content of the oxide fine particles is 0.01 pt.wt. to 20 pts.wt. to 100 pts.wt. glass particles. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an inorganic particle-containing resin composition suitable for production of a display panel member, a transfer film obtained from the composition, and a method for producing a display panel member using the transfer film.

  In recent years, a plasma display has attracted attention as a flat fluorescent display. FIG. 1 is a schematic view showing a cross-sectional shape of an AC type plasma display panel (hereinafter also referred to as “PDP”). In FIG. 1, reference numerals 101 and 102 denote opposing glass substrates, and reference numerals 103 and 111 denote partition walls. Cells are partitioned by the glass substrate 101, the glass substrate 102, the rear partition wall 103, and the front partition wall 111. 104 is a transparent electrode fixed to the glass substrate 101, 105 is a bus electrode formed on the transparent electrode 104 for the purpose of reducing the resistance of the transparent electrode 104, and 106 is an address electrode fixed to the glass substrate 102. It is. 107 is a fluorescent material held in the cell, 108 is a dielectric layer formed on the surface of the glass substrate 101 so as to cover the transparent electrode 104 and the bus electrode 105, and 109 is used to cover the address electrode 106. A dielectric layer is formed on the surface of the glass substrate 102, and 110 is a protective film made of, for example, magnesium oxide. In a color PDP, a color filter (red / green / blue) or a black matrix may be provided between the glass substrate and the dielectric layer in order to obtain a high contrast image.

  As a method for forming the partition walls, electrodes, resistors, phosphors, color filters, black matrix and the like which are PDP members, a photolithography method is suitable. The photolithographic method is to form a layer made of a paste-like photosensitive composition containing inorganic particles and a vehicle on the surface of a substrate or the like, and to form a pattern by exposing and developing the layer, and then firing the pattern. Then, the organic substance is removed and the inorganic particles are sintered. In particular, a photolithography method using a transfer film having a layer formed from the photosensitive composition and transferring it to the surface of a substrate or the like provides a film with excellent thickness uniformity, This is very preferable because work efficiency is improved.

  For example, when the partition is formed by the above-described method, the organic material is removed in the baking process and the film thickness is reduced. Therefore, the transfer layer is about 1.2 to 2.0 times the film thickness of the partition to be formed. It is necessary. Specifically, in order to set the partition wall thickness to 50 to 200 μm, the transfer layer needs to have a thickness of about 50 to 300 μm.

  Here, it is desirable that the partition walls constituting the PDP have a high aspect ratio and a uniform shape from the viewpoint of developing good electrical characteristics. However, if the thickness of the transfer layer is large, the pattern side wall tends to be removed during development, and it is difficult to obtain a partition wall with a uniform and good pattern shape. In addition, if the baking process is performed with the side walls of the pattern removed during development, the pattern may be peeled off or the deformation may be severe.

In order to solve such problems, for example, in a method of manufacturing a PDP barrier rib, the barrier rib forming composition film has a structure in which two or more barrier rib forming compositions having different solubility in a developer are laminated. An invention relating to a method for manufacturing a partition wall for PDP is disclosed (for example, see Patent Document 1).
However, in the method disclosed in Patent Document 1, since the solubility is merely changed by adjusting the copolymer composition ratio of the resin constituting the partition wall forming composition, there is not necessarily a difference in solubility. In some cases, it is not sufficient, and there is still a problem in obtaining a partition wall having a uniform and good pattern shape.

  Therefore, in order to obtain a high aspect ratio and good shape with a single exposure, to suppress light scattering and diffraction at the interface between the inorganic component and the organic component, the refractive index of the organic component and the refraction of the inorganic component in the film Methods to match rates are being considered.

In general, the refractive index of inorganic particles used in this application is about 1.50 to 1.65 even with a low refractive index, and the refractive index of ordinary organic components is about 1.40 to 1.50. is there. Therefore, in order to match the refractive index of the inorganic particles and the refractive index of the organic component, it is necessary to use an organic component having a high refractive index. However, since organic components having a high refractive index have poor thermal decomposability, organic residues remain on the members such as the partition walls after firing, and the members tend to be colored, which makes it impossible to produce a highly reliable display. is there.
JP-A-9-92137

  The present invention is intended to solve the above-mentioned problems, and can form a member having an excellent pattern shape and a high aspect ratio, and is excellent in the combustibility of organic components in the firing process and has a high reliability. An object of the present invention is to provide an inorganic particle-containing resin composition capable of producing

  Another object of the present invention is to provide a transfer film having an inorganic particle-containing resin layer formed from the inorganic particle-containing resin composition and a method for producing a member for a display panel using the transfer film.

  The present inventors have intensively studied to solve the above problems. As a result, the inventors have found that the above problems can be solved by using specific oxide fine particles and matching the refractive index of the inorganic component and the refractive index of the organic component, and have completed the present invention.

That is, the inorganic particle-containing resin composition of the present invention has an average particle diameter in the range of 0.001 to 5 μm, a refractive index in the range of 1.4 to 1.8, and a specific surface area of 0.5. ~ 300m ²
Oxide fine particles, glass powder, alkali-soluble resin and radiation-sensitive component in the range of / g, and the content of the oxide fine particles is 0.01 to 20 parts by weight with respect to 100 parts by weight of the glass powder. It is characterized by.

The transfer film of the present invention has an average particle diameter in the range of 0.001 to 5 μm, a refractive index in the range of 1.4 to 1.8, and a specific surface area of 0.5 to 300 m ² /. Inorganic particles containing oxide fine particles, glass powder, alkali-soluble resin and radiation sensitive component in the range of g, and the content of the oxide fine particles is 0.01 to 20 parts by weight with respect to 100 parts by weight of the glass powder It has a containing resin layer and a support film.

  Further, the method for producing a member for a display panel of the present invention includes a step of transferring an inorganic particle-containing resin layer constituting the transfer film onto a substrate using the transfer film of the present invention, and exposing the inorganic particle-containing resin layer. A step of forming a latent image of the pattern by processing, a step of forming the pattern by subjecting the inorganic particle-containing resin layer to water development, and a step of baking the pattern.

  According to the present invention, the oxide fine particles function as a combustion aid, so that even if a high refractive index organic component is used, the combustibility is excellent, and no organic residue remains on the member obtained using the composition of the present invention. A highly reliable display can be manufactured. Further, since the oxide fine particles function like a high softening point filler, the pattern shape after firing can be maintained, and a member having an excellent pattern shape and a high aspect ratio can be formed. Furthermore, the foam removal property at the time of baking is favorable, and the member without an organic residue can be formed.

Hereinafter, the inorganic particle-containing resin composition, the transfer film, and the method for producing the display panel according to the present invention will be described in detail.
[Inorganic particle-containing resin composition]
The inorganic particle-containing resin composition of the present invention contains oxide fine particles, glass powder, an alkali-soluble resin, and a radiation-sensitive component.

<Oxide fine particles>
The fine oxide particles used in the composition of the present invention have an average particle size of 0.001 to 5 μm, preferably 0.005 to 3 μm, and more preferably 0.02 to 0.3 μm. This average particle diameter is a value sufficiently smaller than the wavelength of ultraviolet rays (for example, g-line: 436 nm, h-line: 405 nm, i-line: 365 nm) used in the exposure process during the manufacturing process of the display panel member. By using oxide fine particles having a particle size in this range, the scattering and reflection of exposure light at the interface between the oxide fine particles and the organic component are negligibly small, and the composition is regarded as an optically homogeneous solution. There is an advantage that can be.

Furthermore, when the specific surface area of the oxide fine particles is in the range of 0.5 to 300 m ² / g,
Scattering of exposure light at the interface between the oxide fine particles and the organic component can be suppressed, and a good partition pattern can be obtained.

  The oxide fine particles used in the composition of the present invention are oxides having a refractive index in the range of 1.4 to 1.8. By using oxide fine particles having a refractive index in this range, there is an advantage that the combustibility of the organic component can be improved while making the refractive index of the inorganic component and the organic component close to each other in the composition.

Preferable examples of the oxide fine particles that can be used in the present invention include silicon oxide, aluminum oxide, and magnesium oxide.
The oxide fine particles are relatively stable and hardly cause reaction on the surface. Further, since the oxide fine particles are commercially available, the cost is low and the supply is stable. The most suitable oxide fine particles can be selected from the functions of the oxide fine particles and the reactivity with the organic components used. Also, a plurality of oxide fine particles may be mixed to match the organic component.

  In the inorganic particle-containing resin composition of the present invention, the oxide fine particles are used in an amount of 0.01 to 20 parts by weight, preferably 0.5 to 15 parts by weight with respect to 100 parts by weight of the glass powder. Use of the oxide fine particles in an amount within the above range is effective in adjusting the thermal expansion coefficient, and is preferable in terms of film-forming properties at the firing temperature, stability of the formed member, and denseness.

<Glass powder>
Examples of the glass powder used in the composition of the present invention include a low melting point glass powder having a heat softening point of 350 to 650 ° C, preferably 400 to 600 ° C. When the thermal softening point of the glass powder is lower than the above range, the glass powder melts at a stage where organic substances such as resin are not completely decomposed and removed in the firing step of the inorganic particle-containing resin layer formed from the composition. End up. Therefore, a part of the organic substance remains in the formed member, and as a result, members such as the dielectric layer and the partition are colored, and the light transmittance may be reduced. On the other hand, when the thermal softening point of the glass powder exceeds the above range, it is necessary to fire at a high temperature, so that the glass substrate is likely to be distorted. Moreover, it is preferable that the glass transition temperature of the said glass powder is 350-550 degreeC.

The average particle diameter of the glass powder is selected in consideration of the shape of the pattern to be produced, but the average particle diameter is preferably 0.001 to 5 μm in view of pattern formation. Moreover, it is preferable on pattern formation that the specific surface area of glass powder is 1-300 m < ² > / g.

  The refractive index of the glass powder is preferably 1.65 or less, more preferably 1.45 to 1.65, and still more preferably 1.50 to 1.60. When the refractive index of the glass powder is within the above range, the straightness of exposure light is improved, and a partition wall pattern having a good shape can be formed.

  The glass powder preferably contains silicon oxide in the range of 5 to 50% by weight, and more preferably in the range of 10 to 30% by weight. Silicon oxide has a function of improving the denseness, strength and stability of the glass and is effective in reducing the refractive index of the glass. In addition, the thermal expansion coefficient can be controlled to prevent peeling due to mismatch with the glass substrate. When the content of silicon oxide is 5% by weight or more, the coefficient of thermal expansion can be suppressed to be small, the occurrence of cracks occurring when baked on a glass substrate can be reduced, and the refractive index can be suppressed to a low level. Moreover, when the content of silicon oxide is 50% by weight or less, the glass transition point and the load softening point can be kept low, and the baking temperature on the glass substrate can be lowered.

  The glass powder preferably contains boron oxide in the range of 10 to 50% by weight, and more preferably in the range of 20 to 45% by weight. When the content of boron oxide is 10% by weight or more, the glass transition point and the load softening point can be kept low, and baking onto the glass substrate can be facilitated. Further, when the content of boron oxide is 50% by weight or less, the chemical stability of the glass can be maintained. Boron oxide is also effective for lowering the refractive index.

  The glass powder preferably contains at least one of barium oxide and strontium oxide so that the total amount is in the range of 1 to 30% by weight, and is contained in the range of 2 to 20% by weight. More preferably. These components are effective in adjusting the thermal expansion coefficient, and have the effect of preventing deformation of the substrate during firing, the effect of imparting electrical insulation, the effect of improving the stability and denseness of the partition walls to be formed, etc. Have. When the content is 1% by weight or more, devitrification due to crystallization of the glass can be prevented, and when the content is 30% by weight or less, the thermal expansion coefficient and the refractive index can be kept small. At the same time, chemical stability can be maintained.

  The glass powder preferably contains aluminum oxide in the range of 1 to 40% by weight. Aluminum oxide has the effect of stabilizing the glass by expanding the vitrification range, and is effective in extending the pot life of the composition. When the content of aluminum oxide is within the above range, the glass transition point and the load softening point can be kept low, and the adhesion to the substrate can be improved.

The glass powder preferably contains at least one of calcium oxide and magnesium oxide so that the total amount is 1 to 20% by weight. These components have the effect of making the glass easier to melt and controlling the thermal expansion coefficient. When the content is 1% by weight or more, devitrification due to crystallization of the glass can be prevented, and when the content is 15% by weight or less, the chemical stability of the glass can be maintained. .

  The glass powder preferably contains an alkali metal oxide of lithium oxide, sodium oxide and potassium oxide in the range of 1 to 20% by weight. Alkali metal oxides have the effect of facilitating control of the thermal softening point and thermal expansion coefficient of glass and lowering the refractive index as glass powder. Since alkali metal oxides may promote ion migration and diffusion, the total amount of 20% by weight or less can maintain the chemical stability of the glass and keep the thermal expansion coefficient small. .

The glass powder may contain zinc oxide, titanium oxide, zirconium oxide and the like in addition to the above components.
<Other inorganic components>
The fired pattern can be colored by adding various metal oxides other than the oxide fine particles to the composition of the present invention. For example, a black pattern can be formed by including a black metal oxide in the range of 1 to 10% by weight in the composition.

  By including at least one, preferably three or more of Cr, Fe, Co, and Mn oxides as the black metal oxide used at this time, blackening becomes possible. In particular, a black pattern can be formed by containing 0.5 wt% or more of Fe and Mn oxides.

  Furthermore, the pattern of each color can be formed by using the composition which added the inorganic pigment which colors red, blue, green, etc. other than black. These colored patterns can be suitably used for a color filter of a plasma display.

<Alkali-soluble resin>
The alkali-soluble resin is not particularly limited as long as it is alkali-soluble, and various resins can be used. Here, “alkali-soluble” refers to the property of being dissolved in the alkali developer to the extent that the desired development processing is possible.

The alkali-soluble resin used in the present invention is preferably a copolymer of a monomer selected from the following monomer (i) and a monomer selected from monomer (ii) and / or monomer (iii). By copolymerizing the monomer (i), alkali solubility can be imparted to the resin. In addition, content of the structural unit derived from monomer (i) is 5 to 90 weight% normally in all the structural units, Preferably it is 10 to 80 weight%, Most preferably, it is 15 to 70 weight%.

As the monomer (i), for example,
Acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, succinic acid mono (2- (meth) acryloyloxyethyl), 2-methacryloyloxyethylphthalic acid Carboxyl such as 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2-acryloyloxypropyl tetrahydrohydrogen phthalate, ω-carboxy-polycaprolactone mono (meth) acrylate Group-containing monomers;
Hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (α-hydroxymethyl) acrylate;
Examples thereof include alkali-soluble functional group-containing monomers represented by phenolic hydroxyl group-containing monomers such as o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene.

Particularly preferred monomers (i) include 2-methacryloyloxyethyl phthalic acid, 2-
Examples include acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, and 2-acryloyloxypropyl tetrahydrohydrogen phthalate.

As the monomer (ii), for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, totyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate Ester (meth) acrylates other than the monomer (i), such as glycidyl (meth) acrylate and dicyclopentanyl (meth) acrylate;
Styrene, α-methylstyrene, α-methylchlorostyrene, α-methylbromostyrene, hydroxymethylstyrene, carboxymethylstyrene, vinylnaphthalene, vinylanthracene, vinylcarbazole, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2 -Aromatic vinyl monomers such as pyrrolidone;
Examples thereof include monomers copolymerizable with the monomer (i) represented by conjugated dienes such as butadiene and isoprene.

Examples of the monomer (iii) include styrene, methyl (meth) acrylate,
Macromonomer represented by a macromonomer having a polymerizable unsaturated group such as (meth) acryloyl group, allyl group, vinyl group at one end of a polymer chain such as ethyl (meth) acrylate and benzyl (meth) acrylate And the like.

  The alkali-soluble resin can be polymerized, for example, by radical polymerization. As an initiator for radical polymerization, azobisisobutyronitrile, benzoyl peroxide, or the like can be used. As a solvent for radical polymerization, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, or the like can be used. The polymerization temperature can usually be carried out at 50 to 100 ° C., and the polymerization time is usually 30 to 600 minutes.

  The polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the alkali-soluble resin is usually 5,000 to 100,000, preferably 8,000 to 50,000. When Mw is in the above range, a PDP member having an excellent pattern shape can be formed. In addition, Mw of alkali-soluble resin can be controlled by the ratio of a monomer and a polymerization initiator, for example.

  The glass transition temperature of the alkali-soluble resin is 20 to 90 ° C, preferably 25 to 75 ° C. When the glass transition temperature is lower than the above range, the coating film tends to be tacky and is difficult to handle. On the other hand, when the glass transition temperature exceeds the above range, the adhesiveness with the glass substrate as the support may be deteriorated and transfer may not be possible. In addition, the said glass transition temperature can be suitably adjusted by changing the quantity of said monomer (i), (ii), (iii).

The acid value of the polymer or oligomer having an acidic group such as a carboxyl group is in the range of 50 to 200, preferably 60 to 180. When the acid value is lower than the above range, the allowable development width tends to be narrowed. Also, if the acid value exceeds the above range, the solubility of the unexposed area in the developing solution will be lowered. Therefore, if the developing solution concentration is increased, the exposed area will be peeled off, and it will be difficult to obtain a high-definition pattern. There is a tendency.

  In the composition of the present invention, the alkali-soluble resin is used in a range of 10 to 50 parts by weight, preferably 15 to 40 parts by weight with respect to 100 parts by weight of the glass powder. By containing the alkali-soluble resin within the above range, a pattern (member) having a good shape can be formed.

<Radiation sensitive component>
In the composition of the present invention, the radiation-sensitive component is used in an amount of 10% by weight or more, preferably 20 to 60% by weight in the organic component from the viewpoint of sensitivity to light. Here, as the radiation sensitive component, there are a light insolubilizing type and a light solubilizing type.

  As a photo-insoluble type, (A) a functional monomer or oligomer having one or more unsaturated groups in the molecule, (B) an aromatic diazo compound, an aromatic azide compound, an organic halogen compound, etc. And (C) a so-called diazo resin such as a condensate of a diazo amine and formaldehyde.

  As a light-soluble type, (D) a complex of a diazo compound with an inorganic acid or an organic acid, a quinone diazo compound, (E) a quinone diazo compound combined with an appropriate polymer binder, such as a phenol resin And naphthoquinone-1,2-diazide-5-sulfonic acid ester.

As the radiation-sensitive component in the present invention, all of the above-mentioned components can be used, but those of the above-mentioned (A) are preferable in that they can be used simply by mixing with inorganic components.
Examples of the photosensitive monomer include a compound containing a carbon-carbon unsaturated bond. Specifically,
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, sec-butyl (meth) acrylate, Iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, allyl (meth) acrylate, benzyl acrylate, butoxyethyl acrylate, butoxytriethylene glycol relate, cyclohexyl (meth) acrylate, di Cyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylic , Heptadecafluorodecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, isodexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl ( (Meth) acrylate, 2-methoxyethyl (meth) acrylate, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, octafluoropentyl (meth) acrylate , Phenoxyethyl (meth) acrylate, stearyl (meth) acrylate, trifluoroethyl (meth) acrylate, aminoethyl (meth) acrylate, phenyl ( Data) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, (meth) acrylates such as thiophenol (meth) acrylate;
Allylated cyclohexyl di (meth) acrylate, 2,5-hexanedi (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate , Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, methoxylated cyclohexyl di (meth) acrylate, neopentyl glycol di (meth) acrylate, Di (meth) taacrylates such as propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, triglycerol di (meth) acrylate;
Pentaerythritol tri (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylolpropane PO modified tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol Polyfunctional (meth) acrylates such as monohydroxypenta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, benzyl mercaptan (meth) acrylate;
A monomer in which 1 to 5 of the aromatic ring hydrogen atoms in the compound are substituted with chlorine or bromine atoms; and
Styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, chlorinated styrene, brominated styrene, α-methylstyrene, chlorinated α-methylstyrene, brominated α-methylstyrene, chloromethylstyrene, hydroxymethyl Examples thereof include styrene, carboxymethyl styrene, vinyl naphthalene, vinyl anthracene, vinyl carbazole, γ-methacryloxypropyltrimethoxysilane, and 1-vinyl-2-pyrrolidone. The said photosensitive monomer may be used individually by 1 type, or may be used in combination of 2 or more type.

In the present invention, a photopolymerization initiator can be used as the radiation-sensitive component. Examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamino) benzophenone, 4,4-dichlorobenzophenone, 4-benzoyl- 4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt- Butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 2,4-diethylthioxanthone, benzyl Methyl ketanol, benzylmethoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methyleneanthrone, 4 -Azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexanone, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o -Methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1- Phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, Michler's ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propan-1-one, 2-benzyl- 2-dimethylamino-1- (4-morpholinophenyl) butanone-1,2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2′-dimethoxy-1,2-diphenylethane-1-one, Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenyl Phosphine oxide, naphthalenesulfonyl chloride, quinolinesulfonyl chloride Rholide, N-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylformine, camphorquinone, carbon tetrabrominated, tribromophenyl sulfone, benzoin peroxide, and And a combination of a photoreductive dye such as eosin or methylene blue and a reducing agent such as ascorbic acid or triethanolamine.

  The said photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more type. The photopolymerizable initiator is generally used in the range of 0.1 to 30 parts by weight, preferably 0.3 to 20 parts by weight with respect to 100 parts by weight of the inorganic particles. In particular, when a combination of a photosensitive monomer and a photopolymerization initiator is used as the radiation-sensitive component, the content of the photosensitive monomer is usually 1 to 100 parts by weight, preferably 5 to 100 parts by weight of the glass powder. It is 50 weight part, and content of a photoinitiator is 1-50 weight part normally with respect to 100 weight part of photosensitive monomers, Preferably it is 2-40 weight part. When content of a radiation sensitive component exceeds the said range, the shape of the member for display panels after baking may deteriorate.

<Ultraviolet absorber>
In the present invention, it is also effective to add an ultraviolet absorber to the composition. By adding a compound having a high ultraviolet absorption effect, a high aspect ratio, high definition, and high resolution can be obtained. As the ultraviolet absorber, an organic dye or an inorganic pigment can be used, and among them, an organic dye or an inorganic pigment having a high UV absorption coefficient in a wavelength range of 350 to 450 nm is preferably used.

  Specifically, organic dyes such as azo dyes, amino ketone dyes, xanthene dyes, quinoline dyes, amino ketone dyes, anthraquinone dyes, benzophenone dyes, diphenyl cyanoacrylate dyes, triazine dyes, p-aminobenzoic acid dyes Inorganic pigments such as dyes, zinc oxide, titanium oxide, and cerium oxide can be used. In these, since organic dye does not remain in the insulating film after firing, it is preferable because the deterioration of the insulating film characteristics can be reduced, but from the viewpoint of the reliability of the flat display panel, zinc oxide, titanium oxide, cerium oxide Such inorganic pigments are more preferred.

  The inorganic pigment can be added in an amount of 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight, with respect to 100 parts by weight of the glass powder. When the amount is less than 0.001 part by weight, the effect of adding the ultraviolet light absorber is reduced. When the amount exceeds 5 parts by weight, the effect of the ultraviolet light absorber is so large that light cannot reach the lower layer of the film, and the pattern cannot be formed. Is not preferable because it may not be maintained.

<Sensitizer>
A sensitizer may be added to the composition of the present invention in order to improve sensitivity. Examples of the sensitizer include 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 2,4-diethylthioxanthone, 2,3-bis (4 -Diethylaminobenzal) cyclopentanone, 2,6-bis (4-dimethylaminibenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone, 4,4-bis (Diethylamino) -benzophenone, 4,4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, 2- (p- Dimethylaminopheny Vinylene) -isonaphthothiazole, 1,3-bis (4-dimethylaminobenzal) acetone, 1,3-carbonyl-bis (4-diethylaminobenzal) acetone, 3,3-carbonyl-bis (7-diethylaminocoumarin) ), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, Examples thereof include 1-phenyl-5-ethoxycarbonylthiotetrazole.

  The above sensitizers may be used alone or in combination of two or more. Some sensitizers can also be used as photopolymerization initiators. The sensitizer can be added in an amount of usually 0.01 to 5% by weight, more preferably 0.05 to 3% by weight, based on the inorganic component. If the amount of the sensitizer is too small, the effect of improving the photosensitivity may not be exhibited, and if the amount of the sensitizer is too large, the residual ratio of the exposed portion may be too small.

<Polymerization inhibitor>
In order to improve the thermal stability during storage, a polymerization inhibitor may be added to the composition of the present invention. Examples of the polymerization inhibitor include hydroquinone, monoesterified hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-tert-butyl-p-methylphenol, Examples include chloranil and pyrogallol. The polymerization inhibitor can be added to the composition in an amount usually ranging from 0.001 to 1% by weight. <Antioxidant>
An antioxidant may be added to the composition of the present invention in order to prevent oxidation of the acrylic copolymer during storage. Examples of the antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-4-ethylphenol, 2,2-methylene-bis- (4 -Methyl-6-tert-butylphenol), 2,2-methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4-bis- (3-methyl-6-tert-butylphenol), 1, 1,3-tris- (2-methyl-6-tert-butylphenol), 1,1,3-tris- (2-methyl-4-hydroxy-tert-butylphenyl) butane, bis [3,3-bis- (4-Hydroxy-3-t-butylphenyl) butyric acid] glycol ester, dilauryl thiodipropionate, triphenyl phosphite and the like. The antioxidant can be added to the composition in an amount usually ranging from 0.001 to 1% by weight.

<Organic solvent>
An organic solvent may be added to the composition of the present invention in order to adjust the viscosity of the solution. Examples of the organic solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methoxypropyl acetate, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, Examples include dimethyl sulfoxide, γ-butyrolactone, bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, and chlorobenzoic acid. The said organic solvent may be used individually by 1 type, or 2 or more types may be mixed and used for it.

<Preparation of inorganic particle-containing resin composition>
The composition of the present invention is usually prepared by mixing three components such as oxide fine particles, glass powder, alkali-soluble resin, radiation-sensitive component and solvent so as to have a predetermined composition, and then homogenizing with three rollers or a kneader. And mixed and dispersed.

  The viscosity of the composition can be adjusted as appropriate depending on the amount of inorganic particles, thickener, organic solvent, plasticizer, precipitation inhibitor, etc., but the range is 2,000 to 200,000 cps (centipoise). It is.

In the composition of the present invention, the average refractive index (hereinafter also referred to as “refractive index R ¹ ”) of the oxide fine particles and glass powder in the composition, and the refraction of an organic component including an alkali-soluble resin and a radiation-sensitive component. The difference from the refractive index (hereinafter also referred to as “refractive index R ² ”) is preferably within ± 0.05, particularly preferably within ± 0.03. Since the difference between the refractive indexes R ¹ and R ² is small, an excellent pattern shape and a pattern with a high aspect ratio can be obtained.

The refractive indexes R ¹ and R ² in the present invention are refractive indexes with respect to exposure light used when forming a display panel member using the composition or transfer film of the present invention.
The refractive index R ¹ is obtained from the following formula.

R ¹ = n ₁ r ₁ + n ₂ r ₂
In the formula, n ₁ and n ₂ represent the volume fraction of oxide fine particles and glass powder, respectively, and r ₁ and r ₂ represent the refractive indexes of the oxide fine particles and glass powder, respectively.

  The refractive index of the oxide fine particles and glass powder can be measured by the Becke method. The wavelength of the light to be measured is accurate in confirming the effect of measuring at the wavelength of the light used in the exposure process described later. Specifically, it is preferable to measure with light having a wavelength of 350 to 650 nm, particularly i-line (365 nm), h-line (405 nm) or g-line (436 nm).

The refractive index R ² is prepared by, for example, preparing a composition comprising organic components excluding inorganic components such as oxide fine particles and glass powder, applying the composition on a glass substrate, and drying at 50 to 100 ° C. for 1 to 30 minutes. And after removing a solvent, it can obtain | require by measuring the refractive index of the obtained resin layer.

As a method for measuring the refractive index R ² , a commonly performed ellipsometry method or V-block method is preferable, and measuring at the wavelength of light used in an exposure step described later is accurate in confirming the effect. Specifically, it is preferable to measure with light having a wavelength of 350 to 650 nm, particularly with h-line (405 nm) or g-line (436 nm).

In addition, it is desirable that the light irradiation conditions at the time of measurement are conditions in which the sample is not photocured. Specifically, the light amount is 0.1 to 50 mW / cm ² , preferably 0.5 to 25 mW / cm ² . The irradiation time is 0.1 to 20 seconds / 1 point, preferably 0.5 to 10 seconds / 1 point.

  In addition, for the measurement of the refractive index after the organic component is polymerized by light irradiation, the same light as in the case of light irradiation to the inorganic particle-containing resin layer formed using the composition of the present invention is used. It can be measured after irradiating and curing the resin layer consisting of only.

[Transfer film]
The transfer film of the present invention contains oxide fine particles, glass powder, alkali-soluble resin and radiation-sensitive component, and oxide fine particles having a refractive index in the range of 1.4 to 1.8 in 100 parts by weight of glass powder. On the other hand, it has an inorganic particle-containing resin layer containing 0.01 to 20 parts by weight and a support film.

  The inorganic particle-containing resin layer has a thickness of 50 to 300 μm, preferably 60 to 200 μm. If the thickness of the resin layer is less than 50 μm, the required thickness cannot be formed by one-time lamination when a partition having a thickness of 40 to 150 μm after firing is formed. Further, if the thickness of the resin layer is larger than 300 μm, the time for exposure and development becomes longer, and the throughput cannot be increased, and in order to obtain a desired thickness, it is necessary to increase the baking shrinkage rate in the thickness direction. This is not preferable because defects during firing are likely to occur.

The refractive index of the inorganic particle-containing resin layer is usually 1.45 to 1.65, preferably 1.50 to 1.60. When the refractive index of the inorganic particle-containing resin layer is within the above range, the straightness of the exposure light is improved by matching the refractive indexes of the glass powder and the inorganic particle-containing resin layer, and a partition pattern having an excellent shape is obtained. Obtainable. The refractive index of the inorganic particle-containing resin layer can be measured according to the measuring method of the refractive index R ² described above.

<Support film>
The support film constituting the transfer film of the present invention is preferably a resin film having heat resistance and solvent resistance and flexibility. Since the support film has flexibility, the paste-like composition can be applied by a roll coater, and the inorganic particle-containing resin layer can be stored and supplied in a state of being wound in a roll shape. In addition, as thickness of a support film, it should just be a range suitable for use, for example, is 20-100 micrometers.

  Examples of the resin that forms the support film include polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, polyfluoroethylene, and other fluorine-containing resins, nylon, and cellulose.

  The surface of the support film on which the member forming material layer is formed is preferably subjected to release treatment. Thereby, when forming the member for display panels, peeling operation of a support film can be performed easily.

  Furthermore, as the protective film layer that may be provided on the surface of the inorganic particle-containing resin layer, a resin film having the same flexibility as the support film can be used, and the surface (in contact with the inorganic particle-containing resin layer) can be used. The surface) may be subjected to a mold release treatment.

<Production method of transfer film>
The transfer film of the present invention is obtained by applying the inorganic particle-containing resin composition of the present invention on the support film to form a coating film, and drying the coating film to form an inorganic particle-containing resin layer. It is done. After drying, it is rolled or laminated with a protective film. In addition, the transfer film of the present invention can also be suitably formed by a method in which the resin layer is formed by applying the composition to each of the support film and the protective film, and the resin layer surfaces are stacked and pressure-bonded. .

  The method for applying the composition onto the support film is not particularly limited as long as it is a method capable of efficiently forming a coating film having a large film thickness (for example, 10 μm or more) and excellent uniformity. Examples include a coating method using a knife coater, a coating method using a roll coater, a coating method using a doctor blade, a coating method using a curtain coater, a coating method using a die coater, and a coating method using a wire coater.

What is necessary is just to adjust suitably the drying conditions of a coating film so that the residual ratio of the solvent after drying may be less than 2 weight%, for example, is a drying temperature of 50-150 degreeC, and is about 0.5 to 30 minutes.
[Method for manufacturing display panel member]
The manufacturing method of the display panel member of the present invention is
Transferring the inorganic particle-containing resin layer constituting the transfer film of the present invention onto a substrate;
A step of exposing the inorganic particle-containing resin layer to form a latent image of a pattern;
It includes a step of forming a pattern by subjecting the inorganic particle-containing resin layer to water development, and a step of baking the pattern.

<Transfer process>
The inorganic particle-containing resin layer of the transfer film of the present invention is transferred to a substrate by lamination.
By using a transfer film, a resin layer having excellent film thickness uniformity can be easily formed, and the film thickness of the formed pattern can be made uniform. Moreover, you may form the laminated body which has a resin layer of n layer (n shows an integer greater than or equal to 2) by repeating transcription | transfer n times using the said transfer film. Or you may form the said laminated body by batch-transferring on the board | substrate using the transfer film in which the laminated body which consists of a resin layer of n layers was formed on the support film.

  An example of a transfer process using a transfer film is as follows. After peeling off the protective film layer of the transfer film used as necessary, the transfer film is overlaid so that the surface of the resin layer is in contact with the surface of the substrate, and this transfer film is thermocompression bonded with a heating roller or the like. As a result, the resin layer is transferred and adhered to the surface of the substrate. The support film is preferably peeled off after the exposure step described below, but may be peeled off before the exposure step.

As the transfer conditions, for example, the surface temperature of the heating roller is 40 to 140 ° C., the roll pressure by the heating roller is 0.1 to 10 kg / cm ² , and the moving speed of the heating roller is 0.1 to 10 m / min. Moreover, the board | substrate may be preheated and the preheating temperature is 40-140 degreeC, for example.

  In the transfer step, surface treatment of the substrate can be performed in order to improve the adhesion between the substrate and the resin layer. As the surface treatment solution used for the surface treatment, silane coupling agents such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, tris- (2-methoxyethoxy) vinylsilane, γ-glycidoxypropyltrimethoxy Silane, γ- (methacryloxypropyl) trimethoxysilane, γ (2-aminoethyl) aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, etc. In an organic solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, etc. to a concentration of 0.1 to 5% It can be used those interpretation. Next, the surface treatment liquid can be uniformly applied onto the substrate with a spinner or the like, and then subjected to surface treatment by drying at 80 to 140 ° C. for 10 to 60 minutes.

Examples of the substrate material used in the present invention include a plate-like member made of an insulating material such as glass, silicone, polycarbonate, polyester, aromatic amide, polyamideimide, and polyimide. If necessary, the surface of the plate-like member may be subjected to a chemical treatment with a silane coupling agent or the like; a plasma treatment; Processing may be performed.

  In the present invention, a glass substrate having heat resistance is preferably used as the substrate. Examples of such a glass substrate include “PD200” manufactured by Asahi Glass Co., Ltd.

<Exposure process>
After the transfer process, exposure is performed using an exposure apparatus. In general, the exposure is performed by mask exposure using a photomask, as in normal photolithography.

As the mask to be used, either a negative type or a positive type is selected depending on the type of the photosensitive organic component. Although the exposure pattern of the exposure mask varies depending on the purpose, for example, 10 to 5
00 μm wide stripes or lattices. Alternatively, a direct drawing method using a red or blue visible laser beam, an Ar ion laser, or the like without using a photomask may be used.

  The surface of the inorganic particle-containing resin layer is selectively irradiated (exposed) with radiation such as ultraviolet rays through an exposure mask to form a pattern latent image on the resin layer. In addition, it is preferable to expose in the state which does not peel the support film coat | covered on the resin layer.

  As the exposure apparatus, a parallel light exposure machine, a scattered light exposure machine, a stepper exposure machine, a proximity exposure machine, or the like can be used. Moreover, when performing exposure of a large area, after applying an inorganic particle-containing resin composition on a substrate such as a glass substrate, exposure is performed while transporting, thereby exposing a large area with an exposure machine having a small exposure area. can do.

  Examples of the active light source used in the exposure include visible light, near ultraviolet light, ultraviolet light, electron beam, X-ray, and laser light. Among these, ultraviolet light is preferable, and as the light source, for example, Low pressure mercury lamp, high pressure mercury lamp, super high pressure mercury lamp, halogen lamp, etc. can be used. Among these, an ultrahigh pressure mercury lamp is suitable.

Exposure conditions vary depending on the coating thickness, but exposure is performed for 0.05 to 1 minute using an ultrahigh pressure mercury lamp with an output of 1 to 100 mW / cm ² . In this case, by using a wavelength filter to narrow the wavelength region of the exposure light, light scattering can be suppressed and pattern formation can be improved. Specifically, pattern formation can be improved by using a filter that cuts off i-line (365 nm) light or a filter that cuts off i-line and h-line (405 nm) light.

<Development process>
After the exposure, the resin layer is developed using the difference in solubility in the developer between the photosensitive part and the non-photosensitive part to form a resin layer pattern. Development methods (for example, dipping method, rocking method, shower method, spray method, paddle method, brush method, etc.) and development processing conditions (for example, developer type / composition / concentration, development time, development temperature, etc.) What is necessary is just to select and set suitably according to the kind of inorganic particle containing resin layer.

  As the developer used in the development step, an organic solvent capable of dissolving the organic component in the inorganic particle-containing resin layer can be used. Further, water may be added to the organic solvent as long as its dissolving power is not lost. When the inorganic particle-containing resin layer contains a compound having an acidic group such as a carboxyl group, development can be performed with an alkaline aqueous solution.

  Since the inorganic particles contained in the inorganic particle-containing resin layer are uniformly dispersed by the alkali-soluble resin, the inorganic particles are simultaneously removed by dissolving the resin with a developer and washing.

  Examples of the alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate, diphosphoric acid phosphate. Potassium hydrogen, sodium dihydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, Examples include potassium borate and aqueous ammonia solution.

As the organic alkali, a general amine compound can be used. Specifically, tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine, diethanolamine, triethanolamine, etc. Can be mentioned.

  The density | concentration of aqueous alkali solution is 0.01 to 10 weight% normally, More preferably, it is 0.1 to 5 weight%. If the alkali concentration is too low, the soluble portion is not removed, and if the alkali concentration is too high, the pattern portion may be peeled off and the non-soluble portion may be corroded. The development temperature during development is preferably 20 to 50 ° C. in terms of process control.

  The alkaline aqueous solution may contain additives such as nonionic surfactants and organic solvents. In addition, after the development process with an alkali developer is performed, a washing process is usually performed.

<Baking process>
In order to burn off the organic substance in the resin layer remaining portion after development, the pattern of the formed resin layer is baked in a baking furnace.

  The firing atmosphere varies depending on the composition and the type of substrate, but firing is performed in an atmosphere of air, ozone, nitrogen, hydrogen, or the like. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used.

  The firing treatment condition requires that the organic substance in the inorganic particle-containing resin layer (residual part) be burned out, and the firing temperature is usually 400 to 1000 ° C. and the firing time is 10 to 90 minutes. In the case of patterning on a glass substrate, baking is performed by holding at a temperature of 450 to 600 ° C. for 10 to 60 minutes.

In addition, you may introduce | transduce a 50-300 degreeC heating process in the said transfer, exposure, image development, and each process of baking for the purpose of drying or preliminary reaction.
By the manufacturing method of the present invention including the above-described steps, display panel members such as partition walls, electrodes, resistors, dielectrics, phosphors, color filters, and black matrices, particularly plasma display panel members can be formed. In addition, the manufacturing method of this invention is preferable as a method of forming a partition or a dielectric material among these.

  The glass substrate having the partition layer obtained by the method of the present invention including the above steps can be used on the front side or the back side of the plasma display. Further, it can be used as a substrate for discharging an address portion of a plasma addressed liquid crystal display.

  After the phosphor is applied between the formed barrier rib layers, the front and back glass substrates are sealed together and sealed with a rare gas such as helium, neon, or xenon, whereby the panel portion of the plasma display can be manufactured. Furthermore, a plasma display can be manufactured by mounting a driver IC for driving.

[Example]
Hereinafter, based on an Example, this invention is demonstrated more concretely. However, the present invention is not limited to these examples.

  First, refractive index measurement method, thermal softening point measurement method, glass transition temperature measurement method, polymer acid value measurement method, specific surface area measurement method, average particle diameter measurement method, evaluation after partition wall pattern development The method, the evaluation method after firing the barrier rib pattern, and the method for measuring the weight average molecular weight (Mw) will be described. The concentration (%) in Examples and Comparative Examples is “% by weight” unless otherwise specified, and “parts” means “parts by weight”.

(Refractive index)
The refractive indexes of the oxide fine particles and the glass powder were measured by a liquid immersion method. The oxide fine particles and the glass powder were immersed in several refractive index immersion liquids, and the refractive index of the immersion liquid when the Becke line generated at the boundary between the particles and the immersion liquid disappeared with an optical microscope was used.

The refractive index of the organic component was measured for light having a wavelength of 405 nm at 23 ° C. by an ellipsometry method after preparing a composition consisting only of the organic component and applying and drying steps.
The refractive index of the inorganic particle-containing resin layer was measured for light having a wavelength of 405 nm at 23 ° C. by an ellipsometry method after preparing a composition comprising an organic component and inorganic particles and applying and drying steps.

(Thermal softening point)
The glass powder was sealed in a sample holder, and heated to 30 to 700 ° C. at 10 ° C./min using a differential scanning calorimeter (“2920NDSC” manufactured by TA Instruments). The temperature of the obtained endothermic peak top was defined as the thermal softening point.

(Glass-transition temperature)
The purified polymer was sealed in a sample holder, and heated to −30 to 350 ° C. at 10 ° C./min using a differential scanning calorimeter (TA Instruments “2920NDSC”). The temperature of the obtained endothermic peak top was defined as the glass transition temperature.

(Polymer acid value)
The acid value of the polymer was measured as follows. A predetermined amount (about 1 g) of the purified and dried polymer was weighed, and about 50 ml of ethanol was added to dissolve the polymer. Using a pH meter (main body "D-54S", electrode "9677-10D", manufactured by Horiba), 0.1N-KOH aqueous solution was dropped while stirring the stirrer, and the neutralization end point (pH = 7) was obtained. It was. This was converted to the number of KOH-mg per 1 g of polymer, and this was used as the acid value of the polymer. The calculation of the acid value of the polymer is (56.1 ×
It was calculated from the amount of KOH aqueous solution used × 0.1) / sampled amount.

(Specific surface area)
Oxidized fine particles were placed on a sample holder and measured by a dynamic constant pressure method using a specific surface area meter ("Gemini V2380" manufactured by SHIMADZU).

(Average particle size)
The average particle size was measured using a Coulter counter method and a laser diffraction scattering particle size distribution device ("MT3300" manufactured by Nikkiso).

(Evaluation of partition pattern after development)
The panel was cut into small pieces and the partition wall cross section shown in FIG. 2 was observed with a scanning electron microscope (“S4200” manufactured by Hitachi, Ltd.) to measure the width and height of the partition wall. ◎ if the width and height are within ± 3μm of the desired standard, ○ if it exceeds the standard ± 3μm and within 5μm, △ if it exceeds the standard ± 5μm and within ± 10μm, and if it exceeds the standard ± 10μm X.

(Evaluation of barrier rib pattern after firing)
The panel was cut into small pieces, and the longitudinal direction and vertical section of the partition walls were observed with a scanning electron microscope ("S4200" manufactured by Hitachi, Ltd.), and the width and height of the partition walls were measured. ◎ if the width and height are the desired standards, ◯ if the width and height are within the standard, △ if it is partly out of the standard, and x if it is outside the standard.

(Measurement of weight average molecular weight)
Mw is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) (“HLC-8220GPC” manufactured by Tosoh Corporation). In addition, the measurement by GPC is "TSK guard column" made by Tosoh as GPC column.
"SuperHZM-M" was used, THF (tetrahydrofuran) was used as a solvent, and the measurement temperature was 40 ° C.

[Synthesis of alkali-soluble resin]
<Synthesis Example 1>
200 parts of propylene glycol monomethyl ether, 50 parts of benzyl methacrylate, 50 parts of 2-methacryloyloxyethylphthalic acid and 1.0 part of azobisisobutyronitrile are charged into an autoclave equipped with a stirrer, and uniformly at room temperature in a nitrogen atmosphere Stir until. Next, polymerization was carried out at 80 ° C. for 4 hours, and the polymerization reaction was further continued at 100 ° C. for 1 hour, followed by cooling to room temperature to obtain a polymer solution. The polymerization rate was 98%, and the Mw of the copolymer precipitated from this polymer solution (hereinafter referred to as “polymer (1)”) was 25,000. The glass transition temperature of this polymer (1) was 60 ° C.

<Synthesis Example 2>
As in Synthesis Example 1, except that 200 parts of propylene glycol monomethyl ether, 50 parts of p-hydroxybenzyl methacrylate, 50 parts of 2-methacryloyloxyethyl phthalic acid and 1.0 part of azobisisobutyronitrile were charged into the autoclave. Thus, a polymer solution was obtained. The polymerization rate was 97%, and the Mw of the copolymer precipitated from this polymer solution (hereinafter referred to as “polymer (2)”) was 25,000. The glass transition temperature of this polymer (2) was 100 ° C.

<Synthesis Example 3>
Polymer solution as in Synthesis Example 1 except that 200 parts of propylene glycol monomethyl ether, 50 parts of benzyl methacrylate, 50 parts of 2-methacryloyloxyethyl phthalic acid and 0.1 part of azobisisobutyronitrile were charged into the autoclave. Got. The polymerization rate was 97%, and the Mw of the copolymer precipitated from this polymer solution (hereinafter referred to as “polymer (3)”) was 200,000. The glass transition temperature of this polymer (3) was 65 ° C.

<Synthesis Example 4>
200 parts of propylene glycol monomethyl ether, 80 parts of benzyl methacrylate, 20 parts of methacrylic acid and 1.0 part of azobisisobutyronitrile were charged into an autoclave equipped with a stirrer and stirred at room temperature until uniform in a nitrogen atmosphere. Next, polymerization was carried out at 80 ° C. for 4 hours, and the polymerization reaction was further continued at 100 ° C. for 1 hour, followed by cooling to room temperature to obtain a polymer solution. The polymerization rate was 99%, and the Mw of the copolymer precipitated from the polymer solution (hereinafter referred to as “polymer (4)”) was 25,000. The glass transition temperature of this polymer (4) was 75 ° C.

[Method of manufacturing partition wall]
A photosensitive inorganic particle-containing resin composition (hereinafter also referred to as “photosensitive paste”) comprising oxide fine particles, glass powder, a radiation-sensitive component, a solvent, and an ultraviolet absorber was prepared as follows. After 25 g of an organic component (see Table 1) is dissolved in 30 g of a solvent PGME (propylene glycol monomethyl ether), 45 g of an inorganic component consisting of oxide fine particles and glass powder (see Table 2) and 0.01 g of an ultraviolet absorber are added, A photosensitive paste was prepared by kneading with a kneader. Table 3 shows the oxide fine particles, glass powder and organic components used.

Abbreviations in Table 1 are as follows.
HDA: 2,5-hexanediol diacrylate TMP: trimethylolpropane PO-modified triacrylate MTPMP: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propan-1-one DMMPB: 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1
DETX: 2,4-diethylthioxanthone PGME: propylene glycol monomethyl ether

  Two sheets of support film (width 200 mm, length 30 m, thickness 38 μm) made of a polyethylene terephthalate (PET) film obtained by subjecting the obtained photosensitive paste to a release treatment in advance are prepared, and a roll coater is used on the support film. A coating film was formed by coating, and the formed coating film was dried at 90 ° C. for 10 minutes to remove the solvent, thereby forming a photosensitive resin layer having a thickness of 90 μm.

Next, the photosensitive resin layers formed on the two PET films were bonded to each other and thermocompression bonded with a heating roller. The pressure bonding conditions were such that the surface temperature of the heating roller was 90 ° C., the roll pressure was 4 kg / cm ² , and the moving speed of the heating roller was 1.0 m / min. In this manner, a photosensitive partition wall forming material layer (thickness: 180 μm) was formed, and the transfer film of the present invention was produced.

Next, the transfer film from which the protective film was peeled was superposed on the surface of the glass substrate for a 6-inch panel, and this transfer film was thermocompression bonded with a heating roller. The pressure bonding conditions were: the surface temperature of the heating roller was 90 ° C., the roll pressure was 4 kg / cm ² , and the moving speed of the heating roller was 1.0 m /
Minutes. As a result, the partition wall forming material layer was transferred and adhered to the surface of the glass substrate. When the thickness of the transferred partition wall forming material layer was measured, it was in the range of 180 μm ± 3 μm.

Next, using a negative chrome mask, the partition wall forming material layer was exposed to ultraviolet rays with an ultrahigh pressure mercury lamp having an output of 25 mJ / cm ² from the upper surface. The exposure amount was 200 mJ / cm ² .
Next, the exposed partition wall forming material layer was developed by applying a 0.3% aqueous solution of monoethanolamine kept at 30 ° C. for 120 seconds in a shower. Then, it washed with water using shower spray, the space part which is not photocured was removed, and the grid | lattice-like partition wall pattern was formed on the glass substrate for back plates.

After the obtained barrier rib pattern was fired to form barrier ribs, the barrier rib patterns were evaluated by SEM observation.
[Examples 1 to 5]
Table 3 shows the results. As shown in Table 3, silicon oxide was used as oxide fine particles. Among Examples 1-5, the partition of Examples 1-3 was the pattern with the best aspect ratio. Also, the evaluation after development was the best in Examples 1 to 3, and no chipping or peeling of the partition walls was observed. Examples 4 and 5 were slightly inferior to Examples 1 to 3 in that the amount of oxide fine particles was slightly higher and the number of chipped partition walls increased, but there was no problem with partition pattern evaluation.

[Examples 6 to 10]
Table 3 shows the results. As shown in Table 3, aluminum oxide was used as oxide fine particles. Among Examples 6-10, the partition of Examples 6-8 was the pattern with the best aspect ratio. Also, the evaluation after development was the best in Examples 6 to 8, and no chipping or peeling of the partition walls was observed. Examples 9 and 10 were inferior to Examples 1 to 3 in that the amount of oxide fine particles was slightly large and the number of partition wall defects increased, but there was no problem with partition pattern evaluation.

Examples 11 and 12
Table 3 shows the results. As shown in Table 3, silicon oxide was used as oxide fine particles. In Examples 11 and 12, there was no problem in the pattern shape after development and the pattern shape after baking. In addition, although some coloring was seen after baking, it was a grade which is satisfactory.

[Comparative Example 1]
As shown in Table 4, the partition walls were produced and evaluated in the same manner as in Example 1 except that the volume ratio of the glass powder and the oxide fine particles was different. In Comparative Example 1, since the volume ratio of the glass powder to the oxide fine particles was 70/30, a large amount of residue was generated after development, and the film was peeled off from the support after firing, chipped, and could not be formed.

[Comparative Example 2]
As shown in Table 4, the partition walls were produced and evaluated in the same manner as in Example 2 except that the particle diameters of the oxide fine particles were different. In Comparative Example 2, the exposure light was scattered on the particle surface, and the desired shape of the partition wall could not be formed.

[Comparative Examples 3 to 5]
As shown in Table 4, the partition walls were produced and evaluated in the same manner as in Example 11 except that oxide fine particles having a high refractive index were used. In Comparative Example 11, in the thick inorganic particle-containing resin layer, the exposure light did not reach the bottom portion, and a partition having a desired shape could not be formed.

It is a schematic diagram which shows the cross-sectional shape of an alternating current type plasma display panel. It is a schematic diagram which shows an evaluation location in evaluation of the partition pattern in an Example.

Explanation of symbols

101 Glass substrate 102 Glass substrate 103 Back partition 104 Transparent electrode 105 Bus electrode 106 Address electrode 107 Fluorescent material 108 Dielectric layer 109 Dielectric layer 110 Protective layer 111 Front partition

Claims (10)

Oxide fine particles having an average particle diameter in the range of 0.001 to 5 μm, a refractive index in the range of 1.4 to 1.8, and a specific surface area in the range of 0.5 to 300 m ² / g, An inorganic particle-containing resin composition comprising glass powder, an alkali-soluble resin and a radiation-sensitive component, wherein the content of the oxide fine particles is 0.01 to 20 parts by weight with respect to 100 parts by weight of the glass powder. .   2. The inorganic particle-containing resin composition according to claim 1, wherein the oxide fine particles are at least one selected from the group consisting of silicon oxide, aluminum oxide, and magnesium oxide.   The inorganic particle-containing resin composition according to claim 1, wherein the glass powder has a refractive index of 1.45 to 1.65.   The difference between the average refractive index of the oxide fine particles and the glass powder and the refractive index of an organic component containing an alkali-soluble resin and a radiation-sensitive component is within ± 0.05. An inorganic particle-containing resin composition.   The inorganic particle-containing resin composition according to claim 1, wherein the glass powder has a heat softening point of 400 to 600 ° C. Oxide fine particles having an average particle diameter in the range of 0.001 to 5 μm, a refractive index in the range of 1.4 to 1.8, and a specific surface area in the range of 0.5 to 300 m ² / g, An inorganic particle-containing resin layer containing a glass powder, an alkali-soluble resin, and a radiation-sensitive component, and the content of the oxide fine particles is 0.01 to 20 parts by weight with respect to 100 parts by weight of the glass powder, and a support film A transfer film comprising:   The transfer film according to claim 6, wherein the inorganic particle-containing resin layer has an average refractive index of 1.50 to 1.65. Using the transfer film according to claim 6 to transfer the inorganic particle-containing resin layer constituting the transfer film onto a substrate;
A step of exposing the inorganic particle-containing resin layer to form a latent image of a pattern;
A method for producing a member for a display panel, comprising: a step of forming a pattern by subjecting the inorganic particle-containing resin layer to water development, and a step of baking the pattern.   9. The method for manufacturing a display panel member according to claim 8, wherein the display panel member is at least one member selected from a partition and a dielectric.   The method for manufacturing a member for a display panel according to claim 8, wherein the display panel is a plasma display panel.

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