WO2008035785A1 - Inorganic-particle-containing resin composition, transfer film, and process for producing member for display panel - Google Patents

Abstract

An inorganic-particle-containing resin composition which can form a member having an excellent pattern shape and a high aspect ratio. It comprises an organic ingredient having excellent combustibility and specific fine oxide particles. It can hence be burned at a low temperature and can form a pattern reduced in burning shrinkage or deformation. It enables a highly reliable display panel to be produced. Also provided are: a transfer film comprising an inorganic-particle-containing resin layer formed from the inorganic-particle-containing resin composition; and a process for producing a member for display panels which comprises using the transfer film.

Description

 Specification

 Inorganic particle-containing resin composition, transfer film, and method for producing display panel member

 Technical field

 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.

 Background art

 In recent years, flat panel displays (hereinafter also referred to as “FPDs”) such as plasma display panels (hereinafter also referred to as “PDPs”) and field emission displays (hereinafter also referred to as “FEDs”) as flat fluorescent displays. .) Is attracting attention. The PDP forms a transparent electrode, encloses an inert gas such as argon or neon between two adjacent glass plates, causes a plasma discharge to light up the gas, and emits a phosphor to display information. Display. On the other hand, FED emits electrons from a cathode into a vacuum by applying an electric field, and irradiates the phosphors on the anode to emit light, thereby causing the phosphors to emit light.

As a method for forming such an FPD dielectric, partition, electrode, resistor, phosphor, color filter, black matrix, and the like, a photolithography method is suitable. The photolithographic method is a method in which a layer made of a paste-like photosensitive composition containing inorganic particles and a vehicle is formed on the surface of a substrate or the like, and this is exposed and developed to form a pattern. In this method, the organic material is removed by firing, and the inorganic particles are sintered. In particular, a photolithography method characterized in that a transfer film having a layer formed from the photosensitive composition is used to transfer to a surface of a substrate or the like, and a film having excellent thickness uniformity is obtained. It is very preferable because the working efficiency is improved.

[0004] When the partition wall is formed by the above-described method, for example, the organic material is removed in the baking process and the film thickness is reduced. Therefore, the transfer layer is 1.2 to 2.0 times the thickness of the partition wall to be formed. It is necessary to set the degree. Specifically, in order to make the partition wall thickness 10-200 111, transfer The thickness of the layer should be about 10 to 300 μm.

 [0005] It is desirable that the partition walls constituting the FPD have a uniform shape with a high aspect ratio from the viewpoint of developing good electrical characteristics. However, if the thickness of the transfer layer is large, the side walls of the pattern are removed in the present image, 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.

 [0006] In order to solve such a problem, for example, in a method for manufacturing a partition wall for PDP, by using a partition wall forming composition characterized in that the partition wall forming composition film includes titanium oxide. In addition, an invention relating to a method for manufacturing a partition wall for PDP that can form a pattern with a high aspect ratio without cracking is disclosed (for example, see Patent Document 1).

 [0007] However, the method disclosed in Patent Document 1 is a method of forming a pattern using a sandblast method, and the number of steps is smaller than that of a photographic method of forming a pattern using a photosensitive paste. In addition to concerns about the addition to the environment, there were problems with the photography method that were not possible!

 [0008] Further, in the same way as described above, in the method for producing a partition wall for PDP, the invention relates to a method for producing a partition wall having high light reflectivity and good strength resistance by using a metal oxide and using a low melting point glass powder. (For example, refer to Patent Documents 2 to 4). However, the effect on shape stability is not clear.

 [0009] On the other hand, development of materials that can be fired at low temperature is underway as part of reducing the environmental burden.

[0010] Currently, in a photolithography method! /, In order to suppress light scattering and diffraction at the interface between an inorganic component and an organic component during pattern formation, the refractive index of the organic component in the film and A method to match the refractive index of inorganic components has been studied! Usually, the refractive index of the inorganic component is higher, so that this method uses a higher refractive index and / or an organic component. 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 are easily colored! / ,! /

Patent Document 1: Japanese Patent Laid-Open No. 2005-310568 Patent Document 2: JP 2002-356351 A

 Patent Document 3: Japanese Patent Laid-Open No. 2001-27802

 Patent Document 4: Japanese Patent Laid-Open No. 2002-82433

 Disclosure of the invention

 Problems to be solved by the invention

 [0011] The present invention is intended to solve the above-described problems, and can form a member having an excellent pattern shape and a high aspect ratio, and an organic component excellent in combustibility and a specific oxidation. Inorganic particle-containing resin composition that can be fired at low temperature by using fine particles, and can form a pattern with less shrinkage and distortion during firing, and can produce a highly reliable display panel. The purpose is to provide.

 [0012] 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. To do.

 Means for solving the problem

 [0013] The present inventors have intensively studied to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by using specific oxide fine particles, blending inorganic components and organic components in a specific ratio, and matching the flammable organic composition. It came to complete.

 That is, the inorganic particle-containing resin composition of the present invention contains oxide fine particles having an average particle size in the range of 0.001 to 5 m, glass powder, an alkali-soluble resin, and a radiation-sensitive component, and is oxidized. The fine particles are contained in the range of 30 to 500 parts by weight with respect to 100 parts by weight of the glass powder! /.

 [0015] Further, the transfer film of the present invention comprises oxide fine particles having an average particle size in the range of 0.001 to 5111, glass powder, an alkali-soluble resin and a radiation-sensitive component, and the oxide fine particles are glass powder. It is characterized by having an inorganic particle-containing resin layer, which is contained in a range of 30 to 500 parts by weight with respect to 100 parts by weight, and a support film.

[0016] Further, the method for producing a display panel member 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. Including a step of exposing the inorganic particle-containing resin layer to form a latent image of a pattern, a step of developing the inorganic particle-containing resin layer to form a pattern, and a step of baking the pattern. It is characterized by.

 The invention's effect

 [0017] According to the present invention, the oxide fine particles work as a combustion aid, so that even if a high refractive index organic component is used, the combustibility is excellent, and the member obtained using the composition of the present invention is organic. There is no residue, and a highly reliable display can be manufactured. In addition, 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 high aspect ratio can be formed. Furthermore, the foam removal property at the time of baking is good, and the layer and member without an organic residue can be formed.

 Brief Description of Drawings

 FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC type plasma display panel.

 FIG. 2 is a schematic diagram showing a cross-sectional shape of a general field emission display. Explanation of symbols

 [0019] 101 glass substrate

 102 Glass substrate

 103 Rear bulkhead

 104 Transparent electrode

 105 bus electrode

 106 Address electrode

 107 Fluorescent substance

 108 Dielectric layer

 109 Dielectric layer

 110 Protective layer

 111 Front bulkhead

 201 glass substrate

 202 glass substrate

203 Insulation layer 204 Transparent electrode

 205 Emmit

 206 force sword electrode

 207 Phosphor

 208 gate

 209 Spacer

 BEST MODE FOR CARRYING OUT THE INVENTION

[0020] Hereinafter, a method for producing an inorganic particle-containing resin composition, a transfer film, and a display panel member 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, alkali-soluble resin, and radiation-sensitive component having an average particle diameter in the range of 0.001 to 5111.

[0022] Further, in the composition of the present invention, the oxide fine particles in the composition are contained in the range of 30 to 500 parts by weight, preferably 50 to 200 parts by weight, with respect to 100 parts by weight of the glass powder. More preferably, when it is contained in the range of 50 to 150 parts by weight, there is a tendency that an excellent pattern shape and a pattern with a high aspect ratio can be obtained.

 <0023> <Oxide fine particles>

 The oxide fine particles used in the composition of the present invention have an average particle size of usually 0.00;! To 5 〃m, preferably 0.005 to 1 〃111, and more preferably 0.02— 0. 3〃m

[0024] This average particle size is sufficiently smaller than the wavelength of ultraviolet rays used in the exposure process (eg, g-line: 436 nm, h-line: 405 nm, i-line: 365 nm) during the manufacturing process of the display panel member. It ’s straight.

 [0025] By using oxide fine particles having an average particle diameter 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 optically homogeneous. There is an advantage that it can be regarded as a simple solution.

[0026] Oxide fine particles that can be used in the present invention include silicon oxide, aluminum oxide, It is characterized by containing at least one selected from the group consisting of zirconium, magnesium oxide, titanium oxide, tin oxide, cerium oxide and zinc oxide. Among these, it is preferable to include at least one selected from the group consisting of silicon oxide, aluminum oxide, magnesium oxide, cerium oxide, tin oxide, and zinc oxide.

[0027] The oxide fine particles may have a surface provided with a conductive coating. For example

, Indium oxide oxide (ITO), antimony oxide doped tin monoxide (ATO), antimony oxide doped / tin oxide coated titanium monoxide (ATO coated titanium oxide), or even doped with Al ³⁺ oxide .

[0028] Further, these are dispersed in a ketone system (for example, methyl ethyl ketone, propylene glycol monomethyl ether acetate, cyclohexanone, etc.) 'alcohol system (for example, isopropyl alcohol, methanol, etc.)' in an aqueous system. It may be provided as

 [0029] The oxide fine particles are relatively stable and hardly cause a reaction on the surface. In addition, since the oxide fine particles are commercially available, the cost is low and the supply is stable. The optimum 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.

 [0030] Here, in the inorganic particle-containing resin composition of the present invention, the oxide fine particles are 30 to 500 parts by weight, preferably 50 to 200 parts by weight, based on 100 parts by weight of the glass powder. More preferably, it is used in the range of 50 to 150 parts. By using the oxide fine particles in an amount within the above range, it is effective in adjusting the thermal expansion coefficient, in terms of application of the baking temperature to the heat resistance of the substrate, stability of the partition walls formed, and denseness. preferable. Moreover, there exists a tendency for the intensity | strength of the flat display panel member obtained after baking to become favorable.

 [0031] In order to produce a desired member by firing at a low temperature from a pattern formed by a photolithography method, the organic component constituting the pattern must have high combustibility, and the pattern in the firing process. It is important that the shape of itself does not easily collapse.

[0032] However, generally, if the combustibility of the organic component is increased, the organic component force S, which is the binder of the inorganic component in the pattern, is burned off at an early stage of the firing process, and therefore the pattern shape The shape collapses easily. In particular, in order to achieve firing at a low temperature, it is generally necessary to lower the softening point of inorganic components such as glass in the pattern, and the pattern shape tends to collapse more easily.

 [0033] The resin composition suitably used in the photographic method of the present invention is characterized in that it contains the oxide fine particles. By including such oxide fine particles, it is possible to achieve both the improvement of the combustibility of the organic components constituting the pattern and the suppression of the collapse of the shape of the pattern itself in the firing process.

 [0034] Although the detailed mechanism is not clear, the oxide particles contained in the resin composition have a combustion promoting effect on the organic component contained in the pattern, thereby improving the combustibility of the organic component. It is presumed that force and also play the role of a filler in the pattern, and therefore suppress the collapse of the pattern shape.

 [0035] <Glass powder>

 The glass powder used in the composition of the present invention has a heat softening point of usually 400 to 550 ° C, preferably 400 to 500. C, more preferably 450 to 500. C, a low melting point glass powder. When the thermal softening point of the glass powder is lower than the above range, the inorganic particles-containing resin layer formed from the above composition is not completely decomposed and removed during the firing process of the resin layer containing inorganic particles! This melts the glass powder. 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, the glass substrate is likely to be distorted because it is necessary to fire at a high temperature. The glass transition temperature of the glass powder is preferably 350 to 550 ° C.

[0036] The average particle size of the glass powder is selected in consideration of the shape of the pattern to be produced. Therefore, the average particle diameter is preferably in the range of 0.001 to 5111 in terms of force pattern formation. The specific surface area of the glass powder is preferably in the range of 1 to 300 m ² / g in view of force pattern formation.

[0037] The glass powder preferably contains silicon oxide in the range of 1 to 50% by weight, and more preferably in the range of 1 to 30% by weight. Silicon oxide is the denseness of glass, In addition to improving the strength and stability, it is also effective in reducing the refractive index of glass. In addition, the thermal expansion coefficient can be controlled to prevent peeling due to mismatch with the glass substrate. When the silicon oxide content is 3% by weight or more, the coefficient of thermal expansion can be kept small, the occurrence of cracks when baked on a glass substrate can be reduced, and the refractive index can be kept low. There is. Further, when the content of silicon oxide is 50% by weight or less, the glass transition point and the load softening point tend to be kept low, and the baking temperature on the glass substrate tends to be lowered.

 [0038] The glass powder preferably contains boron oxide in the range of 1 to 50% by weight, and more preferably in the range of 1 to 30% by weight. When the content of boron oxide is 5% by weight or more, there is a tendency that 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 boron oxide content is 50% by weight or less, the chemical stability of the glass tends to be maintained. Boron oxide is also effective for lowering the refractive index.

 [0039] The glass powder preferably contains aluminum oxide in a range of 0.;! 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 tend to be kept low, and the adhesion to the substrate tends to be improved.

 [0040] The glass powder may contain bismuth oxide, zinc oxide, titanium oxide, zirconium oxide and the like in addition to the above components.

 [0041] <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, by including black metal oxide in the composition in the range of 1 to 10% by weight, a black pattern can be formed with force S.

[0042] The black metal oxide used at this time can be blackened by including at least one, preferably three or more of Cr, Fe, Co, and Mn oxides. In particular, by containing 0.5% by weight or more of Fe and Mn oxides, a blacker pattern is obtained. Can be formed.

 [0043] Further, by using a composition to which an inorganic pigment that develops red, blue, green, or the like in addition to black is added, a pattern of each color can be formed. These colored patterns can be suitably used for FPD color filters.

 [0044] <Al strength resoluble 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 alkaline developer to such an extent that the desired development processing is possible.

 [0045] 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 the following monomer (ii) and / or the following monomer (iii). . By copolymerizing the monomer (i), it is possible to impart alkali solubility to the resin. The content of the structural unit derived from the monomer (i) is usually 5 to 90% by weight, preferably 10 to 80% by weight, particularly preferably 15 to 70% by weight in all the structural units.

 [0046] 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) atariloy oral quichetil), 2-methacrylo

Carboxyl group-containing monomers such as oxahydrohydrogen phthalate, 2-ataryl leuenopropoxyretetrahydrohydrogen phthalate, and ω-carboxypolypropylene mono (meth) acrylate.

 Hydroxyl-containing monomers such as (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, -hydroxymethyl) acrylate;

 ο-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene and other phenolic hydroxyl group-containing monomers;

Methoxypolyethylene glycol mono (meth) acrylate, methoxy polypropylene glycol Monomers containing polyoxyalkylene groups such as rumono (meth) acrylate

 And alkali-soluble functional group-containing monomers represented by the above.

[0047] Particularly preferred monomers (i) include 2-methacryloylquichetyl phthalic acid, 2-atari leuno-chichechinole hydrogen phthalate, 2-atali leuno-roxypropynole hydrogen phthalate, 2- Examples include alitaroyloxypropinorehexahydrohydrogen phthalate and 2- talyloxypropyltetrahydrohydrogen phthalate.

 [0048] As the monomer (ii), for example,

 Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, benzyl (meth) acrylate, phenoxycetyl (meth) acrylate, totyl (meth) acrylate, cyclohexyl (meta) ) Ester (meth) acrylates other than the above monomer (i) such as acrylate, isopolonyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate;

 Aromatic butyl monomers such as styrene, α-methyl styrene, α-methyl chlorostyrene, α-methyl bromostyrene racene, vinylo decanole basorole, γ-methacryloxypropinoretrimethoxysilane, 1-vinyl pyrrole 2-pyrrolidone Kind;

 Conjugates such as butadiene and isoprene

 And monomers that can be copolymerized with the monomer (i), such as

[0049] Examples of the monomer (iii) include, for example, a (meth) atari mouth at one end of a polymer chain such as styrene, methyl (meth) acrylate, ethyl (meth) acrylate, benzyl (meth) acrylate, etc. And macromonomers represented by macromonomers having a polymerizable unsaturated group such as a ruthel group, an aryl group and a bur group.

[0050] The alkali-soluble resin used in the present invention may be a polymer having a polymerizable unsaturated double bond in the side chain.

[0051] As the polymer, a polymer obtained by reacting a polymer having a hydroxyl group with an isocyanate compound having a (meth) taroloyl group is preferably used. Specifically, a copolymer obtained by polymerizing a monomer having at least one carboxyl group in the molecule and an ethylenically unsaturated monomer having at least one hydroxyl group in the molecule (hereinafter referred to as “a copolymer”). , " Preferred is a copolymer obtained by reacting an isocyanate compound having a (meth) atalyleunole group with “copolymer a”! //)) (hereinafter also referred to as “specific copolymer”).

 [0052] Specific examples of the monomer having a carboxyl group used as a copolymerization component of the copolymer a include carboxyl group-containing monomers among the monomers (i). These can be used alone or in combination of two or more.

 [0053] Specific examples of the monomer having a hydroxyl group used as a copolymerization component of the copolymer a include hydroxyl group-containing monomers among the monomers ω. These can be used alone or in combination of two or more.

[0054] Further, for the copolymer a, a copolymerizable monomer copolymerizable with the above monomer may be used as a copolymerization component. Specific examples of the copolymerizable monomer include the monomer (ii) and the monomer (iii). These can be used alone or in combination of two or more.

 [0055] Specific examples of the above-mentioned isocyanate compound having a (meth) atalyloyl group include 2 methacryloyloxychetyl isocyanate (for example, Showa Denko MOI Lens MOI), 2-atari oral ilchichetiliso Examples include those obtained by reacting cyanate (for example, Showa Denko Power Lens AOI) and 1,1 bis (acryloyloxymethyl) ethyl isocyanate (for example, Showa Denko Power Lens BEI). .

[0056] The alkali-soluble resin can be polymerized, for example, by radical polymerization.

[0057] As the radical polymerization initiator, azobisisoptyronitrile, benzoyl peroxide, or the like can be used. As a solvent for radical polymerization, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. can be used.

[0058] The polymerization temperature is usually from 50 to; it can be carried out at 100 ° C, and the polymerization time is usually from 30 to 600 minutes.

Yes

[0059] The polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin measured by gel permeation chromatography (GPC) is usually 5,000-100,000, preferably 10,000- 50,000. When the Mw is in the above range, there is a tendency that an FPD member having an excellent shape of a note can be formed. Alkali soluble The Mw of the resin can be controlled by, for example, the ratio of monomer to polymerization initiator.

[0060] The glass transition temperature of the alkali-soluble resin is usually from 0 to 100 ° C, preferably from 10 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. If the glass transition temperature exceeds the above range, the adhesiveness with the glass substrate as a support may be deteriorated and transfer may not be possible. The glass transition temperature can be appropriately adjusted by changing the amount of the monomers (i), (ii), and (iii) with a force S.

 [0061] The acid value of the polymer or oligomer having an acidic group such as a carboxyl group is usually 50 to 200, preferably 60 to 180. When the acid value is lower than the above range, the image allowable 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 decrease, so if the developing solution concentration is increased, the exposed area will be peeled off and a high-definition pattern will be obtained. There is a tendency to be difficult.

 [0062] In the composition of the present invention, the alkali-soluble resin is 10 to 100 parts by weight with respect to 100 parts by weight of the total of the oxide fine particles and the glass powder (hereinafter also referred to as "inorganic particles"). Preferably it is used in the range of 15 to 50 parts by weight. By containing the alkali-soluble resin within the above range, an FPD member pattern having a good shape tends to be formed.

 [0063] <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.

 [0064] In the composition of the present invention, the radiation sensitive component is 10 to 100 weights with respect to 100 weight parts of the total of the oxide fine particles and the glass powder (hereinafter also referred to as "inorganic particles"). Parts, preferably 15 to 50 parts by weight.

 [0065] By containing the radiation-sensitive component within the above range, an FPD member pattern such as a partition wall having a good shape tends to be formed.

 Here, the radiation-sensitive component includes a light-insolubilized type and a light-solubilized type.

[0067] The photo-insolubilized type is (1) having at least one unsaturated group in the molecule (D1) containing a photosensitive monomer or oligomer, (2) aromatic diazo compound, aromatic azimuth (3) Condensates of diazo amines with formaldehyde, V, so-called diazo resins, and others.

[0068] The photo-soluble type includes (4) a complex of a diazo compound with an inorganic acid or an organic acid, one containing a quinone diazo, and (5) a quinone diazo combined with an appropriate polymer binder. Examples thereof include naphthoquinone 1,2,2 diazide 1,5 sulfonic acid ester of phenol resin.

 [0069] As the radiation-sensitive component in the present invention, the force capable of using all of the above-mentioned components. The component (A) is preferable in that it can be used simply by mixing with an inorganic component. .

 [0070] Examples of the photosensitive monomer (D1) include compounds containing a carbon-carbon unsaturated bond.

 Methyl (meth) acrylate, ethyl (meth) acrylate, n propyl (meth) acrylate, isopropyl (meth) acrylate, n butyl (meth) acrylate, sec butyl (meth) acrylate, sec butyl (meta) ) Atalylate, Isobutyl (meth) acrylate, tert Butinole (meth) acrylate, n Pentyl (meth) acrylate, Arino (meth) acrylate, Benzyl acrylate, Butoxetyl acrylate, Butoxytriethylene Glycol relate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, glycerol (meth)

, 2-hydroxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxylate, laurolinole (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2- (meth) acryloyloxet Tyl 2-hydroxypropyl phthalate, methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, otatafluoropentyl (meth) acrylate, phenoxycetyl (meth) acrylate, stearyl (meth) acrylate, trifluoroethyl (Meth) Atylate, Aminoethyl (Meth) Atylate, Phenyl (Meth) Atarylate, Phenoxetyl (Meth) Atarylate, Benzyl (Meth) Atarylate, 1 Naphthyl (Meth) Atarylate, 2-Naphthyl (Meth) Atari Over door, Chiofuenoru (meth) Atari rate (Meth) atarylates such as;

Arylated cyclohexyl di (meth) acrylate, 2,5 hexane di (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 (meta) ) Atalylate, neopentyl glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, triglycerol di (meth) acrylate, α-phenyl-ω-acrylic Royloxypolyoxyethylene Di (meth) methacrylate such as emissions formaldehyde polycondensate;

Pentaerythritol tri (meth) acrylate, trimethylol propane (meth) acrylate, trimethylol propane ΡΟ modified tri (meth) acrylate, trimethylol propane ΕΟ modified tri (meth) acrylate, dipentaerythritol hexa (meta ) Atallate, dipentaerythritol monohydroxypenta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, benzyl mercaptan (meth) acrylate, etc. Sensory (meth) atarylates;

Among the aromatic ring hydrogen atoms in the above compound; monomers in which! To 5 are substituted with chlorine or bromine atoms; and

Styrene, ρ Methyl styrene, ο Methyl styrene, m Methyl styrene, Chlorinated styrene, Brominated styrene, α-Methyl styrene, Chlorinated α-Methyl styrene, Brominated α-Methyl styrene, Chloromethyl styrene, Hydroxymethyl styrene, Carboxy Examples include methylol styrene, urnaphthalene, buranthracene, burcarbazole, γ-methacryloxypropyltrimethoxysilane, and 1-bul-2-pyrrolidone. The above photosensitive monomers may be used alone or in combination of two or more.

In the present invention, (D2) a photopolymerization initiator can be used as the radiation-sensitive component. Photopolymerization initiators include, for example, benzophenone, ο methyl benzoylbenzoate, 4,4 bis (dimethylamine) benzophenone, 4,4 bis (jetylamino) benzophenone, 4,4-dichlorobenzoic benzophenone, and 4-benzoyl 4-methyldiphen-2-ene. Luketone, Divenge Noreketone, fluorenone, 2, 2-diethoxyacetophenone, 2, 2-dimethoxy-2-phenyl-1, 2-phenylacetophenone, 2-hydroxy-1-methylpropiophenone, p-tert-butyldichloro Acetophenone, thixanthone, 2-methylthioxanthone, 2-cyclothioxanthone, 2 isopropyl thixanthone, 4 isopropyl thixanthone, 1 chloro-4 propyl thixanthone, 2, 4 jetylthioxanthone, benzyldimethinoreketanol, benzyl Noremethoxy ethinoreacetanol, benzoin, benzoin methylol ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-aminoleanthraquinone, / 3-chronoleanthraquinone, anthrone, benzanthrone, dibenzos Ron, Methyleneanthrone, 4 Azidobenzanolacetophenone, 2, 6 Bis (p azidobenzylidene) cyclohexanone, 2, 6 Bis (p-azidobenzylidene) -4-methylcyclohexanone, 2—Phenol , 2-Butadione-2- (o methoxycarboninole) oxime, 1 phenyl propanedione 1 2- (o ethoxycarboninole) oxime, 1, 3 diphenylpropane trione-2- (o ethoxycarboninole) ) Oxime, 1 phenyl 3 ethoxy 1 propanetrione 2— (o benzoinole) oxime, michraketone, 2 methyl-1 [4 (methylthio) phenyl] -2 morpholino 1 propane 1 on, 2 benzyl-2 dimethylamino 1 1- (4-morpholinophenyl) butanone-1, 2-hydroxy-2-methyl-1-phenol propane 1-one, 2, 2'-dimethoxy 1,2 diphenylethane 1-one, bis (2,6 dimethoxybenzoyl) 2, 4, 4 trimethyl-pentylphosphine oxide, 2, 4, 6 trimethylbenzoy Ludiphenylphosphine oxide, bis (2, 4, 6 trimethylbenzoyl) monophenylphosphine oxide, naphthalenesulfurolide, quinolinesulfurolide, N-phenylthioatalidone, 4, 4-azo Bisisobutyronitrile, diphenyldisulfide, benzthiazole disulfide, triphenylformine, camphorquinone, carbon tetrabromide, tribromophenylsulfone, benzoin peroxide, and eosinnyamethylene blue Of a photoreducible dye with a reducing agent such as ascorbic acid or triethanolamine Etc., and the like.

The photopolymerization initiators may be used alone or in combination of two or more. The photopolymerization initiator is usually 0.;! To 30 wt. Per 100 parts by weight of the inorganic particles. Parts, preferably 0.3 to 20 parts by weight. In particular, when a combination of a photosensitive monomer and a photopolymerization initiator is used as a radiation-sensitive component, the content of the photosensitive monomer is usually; 100 to 100 parts by weight, preferably 100 to 100 parts by weight, preferably It is 5 to 50 parts by weight, and the content of the photopolymerization initiator is usually:! To 50 parts by weight, preferably 2 to 40 parts by weight with respect to 100 parts by weight of the photosensitive monomer. When the content of the radiation sensitive component exceeds the above range, the shape of the display panel member after firing may deteriorate.

 [0073] The ratio of the content of the alkali-soluble resin to the content of the photosensitive monomer (hereinafter also referred to as "P / A ratio") is usually;! To 4, preferably 1 to 3. . When the P / A ratio is within the above range, the pattern forming property is excellent, and the strength of the flat display panel member obtained after firing tends to be good.

 [0074] <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, high aspect ratio, high definition, and high resolution tend to be obtained. As the ultraviolet absorber, an organic dye or an inorganic pigment can be used. Of these, organic dyes or inorganic pigments having a high UV absorption coefficient in the wavelength range of 350 to 450 nm are preferably used.

 [0075] Specifically, azo dyes, amino ketone dyes, xanthene dyes, quinoline dyes, amino ketone dyes, anthraquinone dyes, benzophenone dyes, diphenino rescyan acrylate dyes, triazine dyes, p-amino benzoes Organic dyes such as acid dyes and inorganic pigments can be used. Of these, organic dyes are preferred because they do not remain in the insulating film after firing, and can reduce deterioration of insulating film properties!

 [0076] The ultraviolet absorber can be added in an amount ranging from 0.00;! To 5 parts by weight, preferably 0.0;! To 1 part by weight, with respect to 100 parts by weight of the inorganic particles. When the amount of the UV absorber is 0.001 part by weight or less, the effect of adding the UV absorber may be reduced. Do n’t keep it!

 [0077] <Sensitizer>

A sensitizer may be added to the composition of the present invention in order to improve sensitivity. Sensitizer For example, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4 isopropylthioxanthone, 1 chloro-4-propylthioxanthone, 2,4 jetylthioxanthone, 2,3 bis (4-jetyla) Minobenzal) cyclopentanone, 2, 6 bis (4-dimethylaminibenzanol) cyclohexanone, 2, 6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone, 4, 4-bis ( Jetylamino) monobenzophenone, 4,4-bis (dimethylamino) chalcone, 4,4bis (jetylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylamino) Phenylvinyl) isonaphthiazole, 1,3-bis 4-dimethylaminobenzal) acetone, 1,3-carbonorebis (4-jetylaminobenzal) acetone, 3,3-carborurubis (7-jetaminocoumarin), N N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate, isoamyl methylaminobenzoate, 3-phenylthiol, 1-phenol Examples include 2-luo 5-ethoxycarbonylthiotetrazole.

 [0078] The above sensitizers may be used alone or in combination of two or more. Some sensitizers can also be used as photopolymerization initiators. The above sensitizer can be added in an amount usually ranging from 0.0;! To 5% by weight, more preferably 0.05 to 3% by weight with respect to 100 parts by weight of the inorganic particles. If the amount of the sensitizer is too small, the effect of improving the photosensitivity may not be exhibited. If the amount of the sensitizer is too large, the residual ratio S of the exposed area may be too small.

 [0079] <Polymerization inhibitor>

A polymerization inhibitor may be added to the composition of the present invention in order to improve the thermal stability during storage. Examples of the polymerization inhibitor include hydroquinone, monoester of hydroquinone, N-nitrosodiphenylamine, phenothiazine, p-t-butylcatechol, N-phenylnaphthylamine, 2,6-di-tert-butyl-p-methylphenol. , Chloraninore, pyrogallol and the like. The polymerization inhibitor can be added to the composition in an amount usually ranging from 0.001 to; [0080] <Antioxidant>

 An antioxidant may be added to the composition of the present invention to prevent oxidation of the acrylic copolymer during storage.

 [0081] Antioxidants include, for example, 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6 di-t-4 ethenylphenol, 2,2 methylene monobis (4 methyl 6- t-Butylphenol), 2, 2 Methylene monobis (4 ethynole 6- t-Butylphenol), 4, 4 Bis-one (3-Methyl-6-t-Butylphenol), 1, 1,

3-tris mono (2-methyl 6-t-butylphenol), 1, 1, 3-tris mono (2-methyl-

4-hydroxy-1-tert-butylphenol) butane, bis [3,3-bis-1- (4-hydroxy-1-3-butylbutenolide) butyric acid] glycololeestenole, dilaurinoretiodipropionate, And triphenyl phosphite.

 [0082] The antioxidant can be added to the composition in an amount usually in the range of 0.00 ;! to 1% by weight.

 [0083] <Organic solvent>

 An organic solvent may be added to the composition of the present invention in order to adjust the viscosity of the solution.

[0084] Examples of the organic solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethino ethenoleateol, methino cerero sonoleb, ethino cerero sonoleb, butino cererosolve, methoxypropyl acetate, methyl ethyl ketone, Dioxane, Acetone, Cyclohexanone, Cyclopentanone, Isobutyl alcoholone, Isopropyl alcoholone, Tetrahydrofuran, Dimethylsulfoxide, γ-Butyloraton, Bromobenzene, Chlorobenzene, Dibromobenzene, Dichlorobenzene, Bromobenzoic acid, Chlorobenzoate Acid, Ethanol, Ethylene glycol, Propylene glycol, α-Terpineol, β-Tenorepineol, Diethyleneglyconoresimethylenoateol, Diethylene Ricohone Monoethyl Ether, Diethylene Glycol Monobutyl Ether, Diethylene Glycol Mono Methinore Ethenore, Dipropylene Glyco Monore Mino Tenore Ethenore, Dipropylene Glyco Monore Mino Tenore Ethenore, Triethylene Glyco Monore Mono Ethenore Ethenore, Ethylene Glycol Monol Ethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl Ether acetate, diethylene glycol monobutyl ether acetate, ethyl acetate monomethinoate etherate acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, isopropyl acetate, ethyl acetate, cyclohexyl acetate, 3-pentanoate , 2-heptanone, 4-heptanone, xylene, tetramethylbenzene, toluene and the like.

 [0085] The organic solvents may be used singly or in combination of two or more.

[0086] <(E) Organosilane compound>

 The composition of the present invention may contain an organosilane compound for the purpose of improving the dispersibility of the inorganic powder and improving plasticization of the transfer film to be formed. Examples of such organic silane compounds include saturated alkylalkoxysilane compounds represented by the following general formula (1) and silane coupling agents represented by the general formula (2).

 [0087] [Chemical 1]

 [In the formula (1), p is 3 to 20, preferably 4 to; an integer of 16, m is an integer of !! to 3, n is an integer of !! to 3, a is;! To 3 )

 [0089] [Chemical 2]

Y one R― Si―― X _r

 I (2)

(Then η ^π 2η + 3-r

 (In the formula (2), R represents a methylene group or an alkylene group having 2 to 100 carbon atoms; Y represents a vinylol group, an epoxy group, an attaryloxy group, a methacryloxy group, a mercapto group, or an amino group; Represents a hydrolyzable group, r is an integer of 0 to 3, and n is an integer of;!-3.

In the above general formula (1), when a saturated alkylalkoxysilane having a p value of less than 3 is used, the resulting inorganic powder-containing resin layer may not exhibit sufficient flexibility. There is. On the other hand, saturated alkylalkoxysilanes with a p value above 20 have a high decomposition temperature, so organic substances are completely released in the firing process of the resin layer containing inorganic powder. The glass powder may melt at the stage where it is not left, and some organic substances may remain in the formed FPD member.

[0091] Examples of the silane coupling agent represented by the general formula (2) include a bur group-containing silane compound such as butyl trichloro silane, butyl trimethoxy silane, butyl triethoxy silane and butyl triacetoxy silane;

 3-Aminopropyltrimethoxysilane, 3-Aminopropyltriethoxysilane, 3- (2-Aminoethyl) aminopropyltrimethoxysilane, 3-Aminopropyltriethoxysilane, 3- (2-Aminoethyl) Amino group-containing silane compounds such as aminopropylmethyldimethoxysilane;

(Meth) ataryloxy group-containing silane compounds such as diethoxysilane and 3-methacryloxypropyltriethoxysilane; Epoxy group-containing silane compounds such as silane and 2- (3,4-epoxycyclohexyleno) ethinoretrimethoxysilane;

 Examples include mercapto group-containing silane compounds such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.

[0092] The above organosilane compounds may be used alone or in combination of two or more. Among the above silanes, n-butinoretrimethoxysilane, n-decinoletrimethoxysila sadecinoresimethinoremethoxysilane, n-butinoretriethoxysilane, n-decinoretriethoxysilane, n-hexa Decinoletriethoxysilane, n-decenoretinoregetoxysilane, n-hexadesinoretinoletoxysilane, n-butinoretripropoxysilane, n-decenoretipropoxysilane, n-hexadecenoretripropoxysilane Silane, vinylenotrichloronosilane, vinyltrimethoxysilane, butyltriethoxysilane, butyltrioxysilane, 3-methac

[0093] The organosilane compound is usually 10 parts by mass or less, preferably 100 parts by mass of inorganic particles. It is preferably used in an amount of 0.00; If the amount of the organosilane compound is excessive, the viscosity may increase with time when the inorganic powder-containing resin composition is stored.

<Preparation of resin composition containing inorganic particles>

 The composition of the present invention is usually prepared by blending various 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 kneading three mouths. Prepare by mixing and dispersing homogeneously with a machine.

[0095] The viscosity of the composition is a force S that can be appropriately adjusted depending on the amount of addition of inorganic particles, thickener, organic solvent, plasticizer, precipitation inhibitor, etc., and its range is usually 2,000-200, 000c ps (centimeter boise).

[0096] For example, when a transfer film is produced by coating on a support film, the range is 2,000.

— 200, OOOcps (centimeter-boise), preferred <2,000—50, OOOcps (centimeter-boise)

).

 [0097] Also, when applied on a substrate as a printing paste, the range is 2,000-200, 000 cps (centimeter-boise), preferably <30,000-200, OOOcps (centimeter-boise) is there.

 [0098] [Transfer film]

 The transfer film of the present invention contains oxide fine particles having an average particle diameter in the range of 0.001 to 5111, glass powder, an alkali-soluble resin, and a radiation-sensitive component, and the oxide fine particles contain silicon oxide, It is at least one selected from the group consisting of aluminum oxide, zirconium oxide, magnesium oxide, titanium oxide, tin oxide, cerium oxide, and zinc oxide, and the thermal softening point of the glass powder is in the range of 400 to 500 ° C. And the said oxide fine particle is contained in 30-500 weight part with respect to 100 weight part of said glass powders, It has an inorganic particle containing resin layer characterized by the above-mentioned, and a support film.

 [0099] The inorganic particle-containing resin layer has a thickness of usually 10 to 300 Hm, preferably 10 to 200 μm.

[0100] If the thickness of the resin layer is greater than 300, the time during exposure and development becomes longer, and the throughput cannot be increased, and in order to obtain the desired thickness, the firing shrinkage rate in the thickness direction is increased. This is not preferable because defects during firing are likely to occur. [0101] <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.

 [0102] 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 while being wound in a roll. It tends to be possible.

 [0103] The thickness of the support film is, for example, 20 to 100 µm as long as it is in a range suitable for use.

 [0104] Examples of the resin forming the support film include polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polybutyl alcohol, polychlorinated butyl, polyfluoroethylene, and other fluorine-containing resins, nylon, and cellulose. Can be mentioned.

 [0105] The surface of the support film on which the member forming material layer is formed is preferably subjected to a release treatment. Thereby, when forming the member for display panels, peeling operation of a support film can be performed easily.

 [0106] Further, as the protective film layer that may be provided on the surface of the inorganic particle-containing resin layer, a resin film having flexibility similar to that of the support film can be used. A mold release treatment may be performed on the surface in contact with the resin layer.

 <Method for producing transfer film>

 In the transfer film of the present invention, the inorganic particle-containing resin composition of the present invention is applied onto the support film to form a coating film, and the coating film is dried to form an inorganic particle-containing resin layer. Is obtained. After drying, it is rolled or laminated with a protective film. The transfer film of the present invention can also be suitably formed by a method in which the composition is applied to each of the support film and the protective film to form a resin layer, and the resin layer surfaces are overlapped and pressure-bonded. it can.

[0108] As a method of applying the above composition on a support film, any method can be used as long as the film thickness is large (for example, 10 m or more) and a coating film excellent in uniformity can be efficiently formed. It is not limited. For example, coating method using a knife coater, coating using a roll coater Examples thereof include a cloth method, 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.

[0109] The drying conditions of the coating film may be adjusted as appropriate so that the residual ratio of the solvent after drying is within ¾ wt%. For example, at a drying temperature of 50 to 150 ° C, for 0.5 to 30 minutes. Degree

[Method for Manufacturing Display Panel Member]

 The method for producing a display panel member of the present invention includes a step of transferring an inorganic particle-containing resin layer constituting the transfer film onto a substrate, and exposing the inorganic particle-containing resin layer to form a latent image of a pattern. The method includes a step, a step of developing the inorganic particle-containing resin layer to form a pattern, and a step of baking the pattern. Moreover, the printing process may be included.

 [0111] <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 the transfer film, a resin layer having excellent film thickness uniformity can be easily formed, and the film thickness tends to be uniform.

 [0112] Further, a laminate having n layers (n represents an integer of 2 or more) of resin layers may be formed by repeating the transfer n times using the transfer film. Alternatively, the laminate may be formed by transferring a laminate composed of n resin layers onto a substrate using a transfer film formed on a support film.

[0113] An example of the transfer process using the transfer film is as follows.

[0114] 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 by a heating roller or the like. After that, the support film is peeled off from the resin layer. As a result, the resin layer is transferred and adhered to the surface of the substrate.

The [0115] transfer conditions, for example, surface temperature 40 of the heat roller; a 140 ° C, 0. roll pressure by heating the low-La is;! A ~ 10 kg / cm ^2, the moving speed of the heating roller 0. l ~ 10m / min. The preheating temperature at which the substrate may be preheated is, for example, 40 to 140 ° C. [0116] In the transfer step, the surface treatment of the substrate can be applied in order to improve the adhesion between the substrate and the resin layer.

[0117] Examples of the surface treatment solution used for the surface treatment include silane coupling agents such as butyltrichlorosilane, butyltrimethoxysilane, butyltriethoxysilane, tris (2-methoxyethoxy) butylsilane, and _γ -glycidoxy. Provirtrimethoxysilane, γ- (methacrylo

—Aminopropyltriethoxysilane, etc. with an organic solvent such as ethylene glycol monomethylenoatenole, ethyleneglycolmonoethylenoleatenoacetate, methenoreanolenole, ethyl alcohol, propyl alcohol, butyl alcohol, etc. A solution diluted to a concentration of 0.1 to 5% can be used.

 [0118] Next, the surface treatment liquid can be uniformly applied onto a substrate with a spinner or the like, and then dried at 80 to 140 ° C for 10 to 60 minutes for surface treatment.

 [0119] 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 treated with chemicals such as a silane coupling agent; plasma treatment; thin film formation treatment such as ion plating, sputtering, gas phase reaction, or vacuum deposition. It can be pre-treated!

 [0120] 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.

 [0121] <Printing process>

The inorganic particle-containing resin composition of the present invention can be used as a film as described above, but the inorganic particle-containing resin composition can also be used as it is printed on a substrate as a paste. When the inorganic particle-containing resin composition is used as a paste as it is, a glass plate, a ceramic, etc. by an appropriate method such as a screen printing method, a curtain coating method, a roll coating method, a bar coating method, a blade coating method, a die coating method, etc. Apply to various substrates The After coating, in a hot-air drying oven or far-infrared drying oven, for example, temperature 80 ~; at 150 ° C, 5 ~

A tack-free coating can be obtained by drying for about 40 minutes.

[0122] <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 ordinary photolithography.

[0123] As the photomask, either a negative type or a positive type is selected depending on the type of the photosensitive organic component.

 [0124] The exposure pattern of the exposure mask is a stripe or lattice having a force different depending on the purpose, for example, 10 to 500 Hm width.

[0125] 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.

[0126] 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.

[0127] It is preferable that the exposure is performed in a state where the support film coated on the resin layer is not peeled off.

 [0128] 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.

 [0129] Further, when performing exposure of a large area, by applying an inorganic particle-containing resin composition on a substrate such as a glass substrate and then carrying out exposure while transporting, an exposure machine having a small exposure area, A large area can be exposed.

 [0130] 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, and ultraviolet light is particularly preferable. As the light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp, or the like can be used. Among these, an ultrahigh pressure mercury lamp is suitable.

[0131] The exposure conditions are different depending on the coating thickness; exposure is carried out for 0.05 to 1 minute using an ultrahigh pressure mercury lamp with an output of! To 100 mW / cm ² . In this case, by narrowing the wavelength region of the exposure light using a wavelength filter, there is a tendency that light scattering can be suppressed and pattern formability can be improved. Specifically, a filter that cuts off i-line (365 nm) light. Alternatively, there is a tendency that the pattern formability can be improved by using a filter that cuts off i-line and h-line (405 nm) light.

[0132] <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, immersion 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.) Further, it may be selected and set as appropriate according to the type of the inorganic particle-containing resin layer.

[0133] 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. In addition, water may be added to the organic solvent as long as its solubility is not lost! When a compound having an acidic group such as a carboxyl group is present in the inorganic particle-containing resin layer, development can be performed with an alkaline aqueous solution.

[0134] 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 in a developer and washing.

 [0135] 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, and ammonium dihydrogen phosphate. , Potassium dihydrogen phosphate, sodium dihydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium carbonate, sodium carbonate, potassium carbonate, boric acid Inorganic alkaline aqueous solutions such as lithium, sodium borate, potassium borate, and aqueous ammonia can be used. However, it is preferable to use an organic alkaline aqueous solution because the alkaline component can be easily removed during firing.

[0136] As the organic alkali, a general amine compound can be used. Specific examples include tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethinoreamine, dimethinoreamine, trimethinoreamine, monoethinoreamine, jetinoreamine, triethylamine, monoisopropylamine. Min, diisopropylamine, ethanolamine, diethanolamine, triethanolamine and the like. [0137] The concentration of the alkaline aqueous solution is usually from 0.01 to 10% by weight, more preferably from 0.;! To 5% by 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.

 [0138] The development temperature during development is preferably 20 to 50 ° C in terms of process control.

[0139] The alkaline aqueous solution may contain additives such as a noion surfactant and an organic solvent.

 [0140] After the development with an alkali developer, a washing process is usually performed.

Yes

 [0141] <Baking process>

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

 [0142] Firing is performed in an atmosphere of air, ozone, nitrogen, hydrogen, or the like that varies depending on the type of composition and substrate. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used.

 [0143] The firing treatment condition requires that the organic substance in the inorganic particle-containing resin layer (residual part) be burned off. Usually, the firing temperature is 400 to 1000 ° C and the firing time is 10 to 90 minutes. is there. When patterning on a glass substrate, firing is performed at a temperature of 450 to 600 ° C for 10 to 60 minutes. The compositions of the present invention can be fired at lower temperatures, 450-550. C, preferably 480-520. Firing is performed at a temperature of C.

 [0144] A heating step of 50 to 300 ° C may be introduced for the purpose of drying or preliminary reaction during the transfer, exposure, development and firing steps.

[0145] For example, when the inorganic particle-containing pattern is formed on a glass substrate by the above-described method, the paste is further laminated by screen printing and subjected to a patterning process. By laminating the containing resin pattern in an oven or the like at 190 ° C. to 220 ° C., the inorganic particle-containing resin pattern can be laminated without breaking by the solvent contained in the paste to be laminated. This allows two layers to be fired at the same time, thus shortening the firing process. [0146] By the manufacturing method of the present invention including the above steps, members for a display panel such as a partition, an electrode, a resistor, a dielectric, a phosphor, a color filter, and a black matrix can be formed. Of these, the production method of the present invention is preferable as a method of forming a partition or a dielectric.

 [0147] 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 FPD.

 Example

 [0148] In the following, the method for explaining the method of the present invention in more detail by way of examples. The present invention is not limited to these examples.

 [0149] [Synthesis Example 1]

 In a flask equipped with a thermometer, stirrer, dropping funnel, and reflux condenser, 180 parts of propylene glycol monomethyl ether acetate, 30 parts of benzenoremethalate, 2 parts of hydroxypropylmethalate, 20 parts of methacrylic acid, 40 parts of methoxypolyethyleneglycol monometatalylate, 1 part of azobisisobutyronitrile and 3 parts of 2,4-diphenyl-4-methyl-1-pentene were charged and stirred under nitrogen atmosphere until uniform. . After stirring, the mixture was polymerized at 80 ° C. for 4 hours, and the polymerization reaction was further continued at 100 ° C. for 1 hour, and then cooled and controlled at 45 ° C. Thereto, 6.5 parts of 2 methacryloyloxysethyl isocyanate was added dropwise from a dropping funnel over 10 minutes. Thereafter, the mixture was kept at 45 ° C. for 3 hours and then cooled to obtain a polymer solution (alkali-soluble resin 4) having an unsaturated double bond in the side chain. The Mw of this binder resin was 35,000.

 [0150] [Example 1]

 (i) Preparation of inorganic particle-containing resin composition

 (A) 27 parts of titanium oxide (1 0) having an average particle size of 0 · 03 111 as oxide fine particles, (B)

 2

 As a lath powder, Bi O -ZnO-B O -BaO-Al O—SiO glass frit (indefinite shape)

 2 3 2 3 2 3 2

, Softening point 449 ° C) 63 parts, (C) n-butyl methacrylate / 2-hydroxypropyl methacrylate / methacrylic acid / methoxypolyethylene glycol monomethacrylate = 40/15/10/35 (mass) _^0/0) copolymer (Mw = 35000) 18 parts, (D) a sense of the radioactive components, trimethylolpropane Atari rate 7 parts as the photopolymerizable monomer, Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 1.8 parts, 2,4-jetylthioxanthone 0.9 parts as photopolymerization initiator, (E) 3 methacryloxy as organosilane compound Propylmethoxysilane 0.4 parts, other dyes represented by the following formula (3) Dye (3-Methyl-1 Phenol 4 1 (p-Tolyldiazenyl) 1H-Pyrazole 5 Ole) 0 · 02 Inorganic particles-containing resin composition (1) was prepared by kneading 25 parts of propylene glycol monomethyl ether as a solvent and a solvent with a bead mill and then filtering with a stainless mesh (500 mesh, 25 μm diameter). .

[0151] [Chemical 3]

 [0152] (ii) Preparation of transfer film:

 The inorganic particle-containing resin composition (1) prepared in the above (i) was applied onto a support film made of a PET film having a film thickness of 38, m with a release treatment in advance using a blade coater. The transfer film (1) of the present invention was produced by drying at 3 ° C. for 3 minutes to remove the solvent, and forming an inorganic particle-containing resin layer having a thickness of 20 am on the support film.

 [Iii] Transfer process of transfer film:

 Using the transfer film (1) prepared in (ii) above, the transfer film was superposed and thermocompression bonded with a heating roller so that the surface of the inorganic particle-containing resin layer was in contact with the surface of the glass substrate. Here, as the pressure bonding conditions, the surface temperature of the heating roller was 80 ° C., the roll pressure was 0.25 MPa, and the moving speed of the heating roller was 0.5 m / min. As a result, the transfer film was transferred to and adhered to the surface of the glass substrate.

 [Iv] (iv) Exposure step of inorganic particle-containing resin layer · Development step:

The inorganic particle-containing resin layer formed on the glass substrate is exposed to the ghi line (mixed) from the support film with an ultrahigh pressure mercury lamp through an exposure mask (5 cm x 5 cm, L / S = 100/100). A latent image of the pattern was formed on the inorganic particle-containing resin layer. The irradiation amount was 500 mJ / cm ² . After exposure, the support film is peeled off and then 0.3% by mass at a liquid temperature of 30 ° C. The developing process was performed for 30 seconds by a shower method using an aqueous sodium carbonate solution as a developing solution, followed by washing with ultrapure water.

[0155] Thereby, the inorganic particle-containing resin in a portion not irradiated with ultraviolet rays was removed, and an inorganic particle-containing resin pattern (1) was formed.

[0156] (V) Pattern width · Film thickness measurement:

 In the above process, the width and height of the inorganic particle-containing pattern (1) formed on the glass substrate were measured. Let the measured width and height values be L (l) 1 and H (l) —1, respectively.

[0157] (vi) Firing step:

 The glass substrate on which the inorganic particle-containing resin pattern (1) was formed was baked for 90 minutes in a temperature atmosphere of 500 ° C. to obtain a partition wall pattern.

[0158] (vii) Pattern width. Measurement of film thickness:

 In the firing step, the width and height of the partition wall pattern formed on the fired glass substrate were measured. Let the measured width and height values be L (l) 2 and H (l) 2, respectively. Also, peeling and distortion in the fired pattern were evaluated according to the following criteria.

 <Peeling>

 ◯: No peeling was confirmed in the fired pattern, and no peeling was confirmed even after rubbing three times with the fingertip.

 Δ: Peeling was not confirmed in the fired pattern, but the pattern peeled off within 3 times when rubbed with a fingertip.

 X: The pattern after baking peeled off from the board | substrate and pattern formation was not able to be performed.

 <Distortion>

 A: No distortion was observed when the cross section of the pattern after firing was observed with an electron microscope.

 X: Distortion was confirmed when the cross section of the pattern after firing was observed with an electron microscope.

[0159] (viii) Evaluation of residual film rate and shrinkage rate:

The film thickness measurement results of the above (V) and (vii) were applied to the following formulas (I) and (Π), and the remaining film rate and shrinkage rate were calculated. Furthermore, the pattern shapes before and after firing were evaluated according to the following criteria a and b. Table 3 shows the evaluation results. [0160] <Standard a>

 A: Residual film rate is 70% or more

 B: Residual film rate is 50% or more and less than 70%

 C: Remaining film rate is less than 50%

 <Criteria b>

 A: Shrinkage is 70% or more

 B: Shrinkage is 50% or more and less than 70%

 C: Shrinkage rate is less than 50% Residual film rate (%) Shrinkage rate (%)

[0161] L (n) -1: Inorganic particle-containing pattern before firing (n) width (μm)

 L (n) — 2: Width of inorganic particle-containing pattern after firing (n) (μm)

 H (n) -1: Inorganic particle content pattern before firing (n) height (μm)

 H (n) -2: Pattern of inorganic particle content after firing (n) height (μm)

 (ix) Strength measurement:

 An indentation test was performed on the barrier rib pattern formed on the glass substrate fired in the firing step. The test conditions were a microhardness meter, a ΙΟΟιιπιΦ cylindrical indenter, a load speed of 5 mN / s, and a maximum load of lOOOOmN. Table 3 shows the results of strength evaluation based on the following criteria.

 [0162] A force that does not change the pattern shape.

 [0163] ○ Slightly deformed.

 [0164] △ Deformed greatly.

 [0165] The force that could not maintain the X shape.

 [Example 2]

 (i) Preparation of inorganic particle-containing resin composition

(A) As oxide fine particles, Haccho 0 coated titanium oxide with an average particle size of 0 iO) 36 parts, (B) Bi O -ZnO-B O- BaO- Al O- SiO

2 2 3 2 3 2 3 2 Rusfrit (Amorphous, Softening point 477 ° C) 54 parts, (C) Benzyl methacrylate / 2-hydroxyethyl methacrylate / methacrylic acid / methoxypolyethylene glycol monomethacrylate as alkali-soluble resin rate = 40/15/15/30 (mass _^0/0) copolymer (Mw = 35000) 13 parts, (D) a sense of the radioactive component, 6 parts of trimethylolpropane Atari rate as the photopolymerizable monomer, tri Propylene glycol ditalylate 6 parts Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 1.8 parts 2,4-ethylthioxanthone 0.9 parts (E) Organosilane compound As a bead mill, 0.4 parts of methacryloxypropyl methoxysilane, 0.15 parts of the above dyes as other optional components, and 125 parts of propylene glycol monomethyl ether as a solvent After kneading, stainless mesh (500 mesh, 25 m diameter) by filtering, the inorganic particles-containing resin composition (2) was prepared.

 [0167] (ii) Each evaluation

 A partition wall pattern was formed and evaluated in the same manner as in Example 1 except that the inorganic particle-containing resin composition (2) prepared in (i) was used. Table 3 shows the evaluation results.

 [0168] [Example 3]

 (i) Preparation of inorganic particle-containing resin composition

 (A) As oxide fine particles, tin oxide with an average particle size of 0 · 03 111 (10) 36 parts, (B) glass

 2

 Bi O -ZnO-B O BaO— Al O SiO-based glass frit (indefinite shape,

 2 3 2 3 2 3 2

(Softening point 477 ° C) 54 parts, (C) Benzylmetatalylate / 2 Hydroxetyl metaltalate / Methacrylic acid / Methoxypolyethylene glycol monometatalate = 40/15/15/30 as alkali-soluble resin (mass _^0/0) copolymer (Mw = 35000) 18 parts of (D) sensitive radiation components, as the photopolymerizable monomer alpha - phenyl - omega - Atari Roy Ruo carboxymethyl polio key sheet ethylene formaldehyde polycondensate (For example, KAYARD R-71 2 manufactured by Nippon Kayaku Co., Ltd.) 7 parts, Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide as a photopolymerization initiator 1.8 parts 2,4-Jetylthioxanthone 0.9 Part (ii) Bead mill of 0.4 part of 3-methacryloxypropylmethoxysilane as organosilane compound, 0.1 part of the above dye as an optional component, and 125 parts of propylene glycol monomethyl ether as solvent After kneading, the mixture was filtered with a stainless mesh (500 mesh, 25 μm diameter) to prepare an inorganic particle-containing resin composition (3).

[0169] (ii) Each evaluation

 A partition wall pattern was formed and evaluated in the same manner as in Example 1 except that the inorganic particle-containing resin composition (3) prepared in (i) was used. Table 3 shows the evaluation results.

[0170] [Example 4]

 (i) Preparation of inorganic particle-containing resin composition

 (A) As oxide fine particles, tin oxide with an average particle size of 0 · 03 111 10) 45 parts, (B) glass

 2

 Bi O -ZnO-B O -BaO-Al O SiO-based glass frit (amorphous,

 2 3 2 3 2 3 2

 (Softening point 477 ° C) 45 parts, (C) Benzylmetatalylate / 2 Hydroxetylmetatalylate / Methacrylic acid / Methyl methacrylate = 60/15/15/10 (mass%) as alkali-soluble resin Copolymer (Mw = 35000) 18 parts, (D) Radiation sensitive component, photopolymerizable monocondensate (for example, KAYARD R-712 manufactured by Nippon Kayaku Co., Ltd.), bis ( 2,4,6-Trimethylbenzoyl) -phenylphosphine oxide 1.8 parts 2,4-dimethylthioxanthone 0.9 parts (E) 3 methacryloxypropyl methoxysilane as organosilane compound 0.4 part, 1, 7- After kneading 0.5 parts of bis (4-hydroxyphenyl) -1,6-hexadiene-3,5-diene and 125 parts of propylene glycol monomethyl ether as a solvent in a bead mill, By filtering with mesh, 25 m diameter) Inorganic particles-containing resin composition (4) was prepared.

 [0171] (ii) Each evaluation

 A partition wall pattern was formed and evaluated in the same manner as in Example 1 except that the inorganic particle-containing resin composition (4) prepared in (i) was used. Table 3 shows the evaluation results.

 [Example 5]

 (i) Preparation of inorganic particle-containing resin composition

 (A) As oxide fine particles, tin oxide with an average particle size of 0 · 03 111 10) 45 parts, (B) glass

 2

 Bi O -ZnO-B O -BaO-Al O SiO-based glass frit (amorphous,

 2 3 2 3 2 3 2

(Softening point 477 ° C) 45 parts, (C) 12 parts of alkali-soluble resin 4 as alkali-soluble resin, (D) Among the radiation-sensitive components, as a photopolymerizable monomer, α-phenyl-ω-attalyloyloxypolyoxyethylene formaldehyde polycondensate (for example, Nippon Kayaku Co., Ltd. RD RD R-712), 6 parts, trimethylolpropane 6 parts of triatalylate, as photopolymerization initiator Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 2 · 7 parts 2,4-dimethylthioxanthone 0.9 parts (Ε) As organosilane compound 3-Methacryloxypropyl methoxysilane 0.4 parts, 1,7-bis (4-hydroxyphenyl) -1,6-dibutadiene as an optional component 0.5 parts of butadiene-3,5-dione, and propylene as solvent After kneading 125 parts of glycol monomethyl ester with a bead mill, the mixture is filtered with a stainless mesh (500 mesh, 25 mm diameter) to obtain a resin composition containing inorganic particles. 5) was prepared.

 [0173] (ii) Each evaluation

 A partition wall pattern was formed and evaluated in the same manner as in Example 1 except that the inorganic particle-containing resin composition (5) prepared in (i) was used. Table 3 shows the evaluation results.

 [Example 6] to [Example 21] and [Comparative Example ;!] to [Comparative Example 4]

 A partition wall pattern was formed and evaluated in the same manner as in Example 1 except that each composition shown in Tables 3 to 5 was used. Tables 3 to 5 show the evaluation results.

 [0175] [Example 22]

 (i) Preparation of inorganic particle-containing resin composition

 (A) As oxide fine particles, Haccho 0 coated titanium oxide with an average particle size of 0 · 03 111 (Haccho 0—Cho iO) 36 parts, (B) As glass powder, Bi O —ZnO—B O—BaO—Al O — SiO-based gas

2 2 3 2 3 2 3 2 Rusfrit (Amorphous, Softening point 477 ° C) 54 parts, (C) Benzyl methacrylate / 2-hydroxyethyl methacrylate / methacrylic acid / methoxypolyethylene glycol monomethacrylate as alkali-soluble resin rate = 40/15/15/30 (mass _^0/0) copolymer (Mw = 35000) 13 parts, (D) a sense of the radioactive components, as the photopolymerizable monomer alpha _ phenyl _ omega - Atariroi Noreokishi Polyoxyethylene formaldehyde polycondensate (eg Nippon Kayaku Co., Ltd. YARD R-712) 12 parts, Bis (2,4,6_trimethylbenzoyl) -phenylphosphine oxide 1.8 parts as photopolymerization initiator 0.9 parts of 2,4-jetylthioxanthone (E) 0.4 parts of 3-methacryloxypropylmethoxysilane as an organic silane compound, 0.15 parts of the above dye as an optional component, and diethylene glycol as a solvent Monoechiruete The inorganic particle-containing resin composition (A) was prepared by kneading 21 parts of lacetate with three rolls.

 [0176] (ii) Screen printing process:

 The prepared inorganic particle-containing resin composition (A) was applied on the entire surface of a glass substrate using a 200 mesh polyester screen and dried at 100 ° C for 10 minutes in a hot air drying oven.

. As a result, a tack-free coating (A) was obtained on the glass substrate.

[0177] Thereafter, through the same steps as those in Example 1 (iv) and subsequent steps, a partition wall pattern was formed and evaluated. Table 5 shows the evaluation results.

[0178] [Table 1]

Table 1. Fine oxide particles

 [0179] [Table 2]

Table 2. Alkali-soluble resins

 nBMA n-Butyl methacrylate

 BzMA benzyl methacrylate

 PEGMA methoxy polyethylene glycol monomethacrylate

 2-HPMA 2-hydroxypropyl methacrylate

 HEMA 2—Hydroxyethyl methacrylate

 MAA methacrylic acid

 MMA Methyl methacrylate

 MOI 2-methacryloxetyl isocyanate

[0180] [Table 3] S 3 .Inorganic particle-containing resin composition and evaluation result 1

 [0181] [Table 4]

 4 2

 [0182] [Table 5]

 5 3

 (Explanation of abbreviations in Table 35)

TMBPPO: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide DETX: 2,4-Getinorethioxanthone

TMPTA: Trimethylolpropane triatrate

TPGDA: Tripropylene glycol ditalylate

 R-712: a-phenyl-ω-acryloyloxypolyoxyethylene formaldehyde polycondensate

PGME: Propylene glycol monomethyl ether

 DEGMEA: Diethyleneglycolenomonochinenoreethenoreacetate

 MPDP: 3-methyl-1-phenyl-4- (ρ-tolyldiazenyl) -1H-pyrazol-5-ol

HPHD: 1,7-bis (4-hydroxyphenyl) -1,6-hexabutadiene-3,5-dione

Claims

The scope of the claims  [1] An inorganic particle-containing resin composition comprising oxide fine particles (A), glass powder (B), alkali-soluble resin (C) and radiation-sensitive component (D),  The oxide fine particles (A) have an average particle size in the range of 0.001 to 5 m, and the oxide fine particles (A) are silicon oxide, aluminum oxide, zirconium oxide, magnesium oxide, titanium oxide, tin oxide. , At least one selected from the group consisting of cerium oxide and zinc oxide,  Thermal softening point force S of the glass powder (B) is in the range of 400-500 ° C,  An inorganic particle-containing resin composition, wherein the oxide fine particles (A) are contained in an amount of 30 to 500 parts by weight with respect to 100 parts by weight of the glass powder (B). [2] The alkali-soluble resin (C) and the radiation-sensitive component (D) are 10 to 100 parts by weight with respect to a total of 100 parts by weight of the oxide fine particles (A) and the glass powder (B); 2. The inorganic particle-containing resin composition according to claim 1, wherein the resin composition is contained within a range of parts by weight! /. [3] A transfer film comprising a layer comprising the inorganic particle-containing resin composition according to claim 1 or 2 and a support film. [4] A method for producing a member for a display panel, comprising the steps of (I) to (IV) below using the transfer film according to claim 3.  (I) Step of transferring the inorganic particle-containing resin layer constituting the transfer film onto the substrate  (II) A step of exposing the inorganic particle-containing resin layer to form a latent image of a pattern  (III) A step of developing the inorganic particle-containing resin layer to form a pattern  (IV) A step of firing the pattern  5. The method for producing a member for a display panel according to claim 4, wherein in the step (IV), the firing temperature is 450 to 600 ° C. 6. The display panel member manufacturing method according to claim 4 or 5, wherein the display panel member member is at least one member selected from the group consisting of an electrode, a partition, and a dielectric.