JP2011064864A - Photosensitive composition, method of forming pattern, and method of manufacturing electrode for fpd - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition forming a precise pattern with a low resistance. <P>SOLUTION: The photosensitive composition contains: (A) conductive particles; (B) glass particles; (C) a compound obtained by reacting an unsaturated carboxylic acid and a carboxylic acid anhydride with an aromatic epoxy resin; (D) an ethylenically unsaturated group containing compound; and (E) a photopolymerization initiator. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photosensitive composition, a pattern forming method, and a method for producing an electrode for a flat panel display. More specifically, the present invention relates to a photosensitive composition used when manufacturing a member of a display panel such as a flat panel display, a member of an advanced mounting material of an electronic component, and a member of a solar cell, and a pattern using the composition. The present invention relates to a forming method and a method for manufacturing an electrode for a flat panel display using the pattern forming method.

  In recent years, there is an increasing demand for higher density and higher definition for pattern processing in circuit boards and display panels. Among such display panels that have been increasing in demand, particularly flat panel displays (hereinafter referred to as “FPD”) such as plasma display panels (hereinafter also referred to as “PDP”) and field emission displays (hereinafter also referred to as “FED”). ) Is attracting attention.

  FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC type PDP. In FIG. 1, 101 and 102 are glass substrates opposed to each other, 103 and 111 are partition walls, and cells are partitioned by the glass substrate 101, the glass substrate 102, the back 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. Reference numeral 107 denotes a phosphor held in the cell, 108 denotes 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 denotes a cover so as to cover the address electrode 106. A dielectric layer formed on the surface of the glass substrate 102, 110 is a protective layer made of, for example, magnesium oxide.

  In a color FPD, 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.

  In the PDP having the above-described configuration and the FPD represented by the FED shown in FIG. 2, the panel has been increased in size and definition, and accordingly, improvement of the pattern processing technique is demanded. However, with the increase in size and definition of such panels, there is a problem that the demand for pattern accuracy becomes very strict, and the screen printing method that is a conventional method cannot be used.

  Therefore, at present, pattern formation by photolithography is mainly used. For example, when manufacturing an electrode, a large-size and high-definition problem that cannot be dealt with by the screen printing method by using a photosensitive paste containing conductive particles such as silver and aluminum in the photolithography method. Pattern formation is possible (see, for example, Patent Documents 1 and 2).

  However, since silver is a noble metal, it is expensive. For this reason, the photosensitive silver paste is also an expensive conductive paste. Moreover, as a defect of the photosensitive silver paste, there is a property that migration occurs in a high-temperature and high-humidity environment, and sulfidation occurs on the silver surface.

  In addition, since aluminum that has been used in recent years as inorganic particles to replace expensive silver is more easily oxidized than silver, there is a problem that the resistance value of the pattern increases in the firing step.

JP 09-306343 A JP-A-10-273338

  The present invention seeks to solve the problems associated with the prior art as described above. That is, an object of the present invention is to provide a photosensitive composition having a low resistance value and capable of forming a high-definition pattern. Another object of the present invention is to provide a pattern forming method using the photosensitive composition and a method for producing an FPD electrode.

  The present inventors have intensively studied to solve the above problems. As a result, in the conventional photosensitive composition, it was common to use an acrylic resin (see Patent Documents 1 and 2) or a cellulose resin as a binder resin, but when these resins are used, It was found that the resistance value of the pattern increased in the firing process.

  The present inventors conducted further studies based on the above findings. As a result, it was found that the above problems can be solved by using a compound obtained by reacting an unsaturated carboxylic acid and a carboxylic anhydride with an aromatic epoxy resin as a binder resin, and the present invention has been completed. .

That is, the present invention relates to the following [1] to [9].
[1] (A) conductive particles, (B) glass particles, (C) a compound obtained by reacting an aromatic epoxy resin with an unsaturated carboxylic acid and a carboxylic anhydride, (D) ethylenically unsaturated A photosensitive composition comprising a group-containing compound and (E) a photopolymerization initiator.

  [2] In the component (C), the aromatic epoxy resin is at least one polyphenol compound selected from bisphenol A, bisphenol F, 4,4′-dihydroxybiphenyl, phenol novolac and cresol novolac, and epichlorohydrin; The photosensitive composition as described in [1] above, which is a compound obtained by reacting

  [3] In the component (C), the unsaturated carboxylic acid is at least one selected from acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid and cinnamic acid. The photosensitive composition as described in [1] or [2] above, wherein

  [4] In the component (C), the carboxylic acid anhydride is selected from maleic anhydride, itaconic anhydride, citraconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, and pyromellitic anhydride. The photosensitive composition according to any one of [1] to [3], wherein the photosensitive composition is at least one.

  [5] The above [1] to [4], wherein the conductive particles (A) are at least one metal-based powder selected from aluminum powder, aluminum alloy powder and aluminum complex powder. The photosensitive composition as described in any one of these.

  [6] The conductive particles (A) and the glass particles (B) are contained in a total amount of 35 to 75% by weight with respect to the entire photosensitive composition. The photosensitive composition as described in any one of [5].

  [7] The photosensitive composition according to any one of [1] to [6], which is a material for forming an electrode for a flat panel display.

  [8] (1) A step of forming a photosensitive resin layer made of the photosensitive composition according to any one of [1] to [7] on a substrate, (2) An exposure treatment of the resin layer. Forming a pattern latent image, (3) forming a pattern by developing the resin layer on which the pattern latent image is formed, and (4) baking the pattern. A characteristic pattern forming method.

  [9] A method for producing an electrode for a flat panel display, comprising producing an electrode by the pattern forming method according to [8].

  According to the present invention, a photosensitive composition having a low resistance value and capable of forming a high-definition pattern is provided. Moreover, according to this invention, the pattern formation method using the said photosensitive composition and the manufacturing method of the electrode for FPD are provided.

  Since the photosensitive composition of the present invention has the above-mentioned properties, it is suitably used as a forming material for display panel members such as FPDs, members for highly mounting materials for electronic components, and members for solar cells, particularly for electrodes. can do.

FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC type PDP. FIG. 2 is a schematic diagram showing a cross-sectional shape of a general FED.

  Hereinafter, the photosensitive composition, the pattern forming method, and the FPD electrode manufacturing method of the present invention will be described in detail including preferred embodiments. In the following description, the layer before exposure formed using the photosensitive composition is referred to as “photosensitive resin layer”, and the pattern obtained by exposing and developing the resin layer and the pattern after baking are collectively referred to. It is also simply called “pattern”.

[Photosensitive composition]
The photosensitive composition of the present invention is obtained by reacting an unsaturated carboxylic acid and a carboxylic acid anhydride with (A) conductive particles, (B) glass particles, and (C) aromatic epoxy resin described below. A compound (hereinafter also referred to as “specific aromatic resin”), (D) an ethylenically unsaturated group-containing compound, and (E) a photopolymerization initiator. The photosensitive composition of the present invention may contain other additives in addition to the above components.

<< Conductive Particles (A) >>
As the conductive particles (A), aluminum powder; aluminum alloy powder; powder made of aluminum complex; metal powder such as Pt, Au, Ag, Cu, Sn, Ni, Fe, Zn, W, Mo; Pt, Au, Examples thereof include powders made of metal compounds such as Ag, Cu, Sn, Ni, Fe, Zn, W, and Mo.

  In these, the at least 1 sort (s) of metal type powder selected from the powder which consists of aluminum powder, aluminum alloy powder, and an aluminum complex is preferable. Moreover, the metal-based powder may be included with a fatty acid. Such metal-based powder or metal-based powder clathrated with a fatty acid is suitable for forming an electrode constituting a display panel such as an FPD.

  Examples of the aluminum alloy powder include Al-Cu alloy powder, Al-Mg alloy powder, Al-Sn alloy powder, Al-Cu-Si alloy powder, Al-Si alloy powder, Al-Si-Mg alloy powder. Alloy powder, Al-Mn alloy powder, Al-Mg-Mn alloy powder, Al-Zn-Mg alloy powder, Al-Zn-Mg-Cu alloy powder, Al-Si-Cu-Mg alloy powder, Al-Cu-Ni-Mg alloy powder, Al-Si-Cu-Ni-Mg alloy powder, etc. are mentioned.

Examples of the aluminum complex include acetylacetone aluminum complex.
Examples of the fatty acids include butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, palmitoyl acid, margaric acid, stearic acid, oleic acid, vaccenic acid, linoleic acid Examples include acids, linolenic acid, nonadecanoic acid, arachidic acid, arachidonic acid, behenic acid, lignoselenic acid, nervonic acid, serotic acid, montanic acid, melicic acid and the like. In order to clathrate the metal powder with the fatty acid, a fatty acid may be added as a grinding aid during the grinding treatment of the metal powder.

The 50% by weight average particle diameter (D50) of the conductive particles (A) is preferably 2 to 20 μm, more preferably 2 to 15 μm, and further preferably 2 to 10 μm. When D50 is in the above range, the exposure light in the exposure step can sufficiently reach the bottom of the photosensitive resin layer, and a high-definition pattern can be obtained. In the present invention, the average particle diameter is a value measured by a laser diffraction / scattering particle size distribution measuring method, and the same applies to other powders. D50 refers to the particle size of a powder having a particle size distribution, in which the powder is accumulated from those having a small particle size, and the cumulative amount is 50% by weight of the total powder amount.
The shape of the conductive particles (A) is not particularly limited, but is preferably spherical, flaky or indeterminate, and more preferably spherical or flaky.

<< Glass particles (B) >>
In the present invention, glass particles (B) are used from the viewpoint of pattern adhesion to a substrate (eg, glass substrate) and adhesion between conductive particles (A). The glass particles (B) can be appropriately selected according to the use of the pattern formed by the photosensitive composition of the present invention (FPD member, electronic component advanced mounting material member, etc.).

As a preferable specific example of the glass particles (B),
1. A mixture of lead oxide, boron oxide and silicon oxide (PbO—B ₂ O ₃ —SiO ₂ system);
2. A mixture of zinc oxide, boron oxide and silicon oxide (ZnO—B ₂ O ₃ —SiO ₂ system);
3. A mixture of lead oxide, boron oxide, silicon oxide and aluminum oxide (PbO—B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ system);
4). A mixture of lead oxide, zinc oxide, boron oxide, silicon oxide (PbO—ZnO—B ₂ O ₃ —SiO ₂ system);
5. Mixture of bismuth oxide, boron oxide and silicon oxide (Bi ₂ O ₃ —B ₂ O ₃ —SiO ₂ system);
6). A mixture of zinc oxide, phosphorus oxide and silicon oxide (ZnO—P ₂ O ₅ —SiO ₂ system);
7). A mixture of zinc oxide, boron oxide and potassium oxide (ZnO—B ₂ O ₃ —K ₂ O system);
8). Mixture of phosphorus oxide, boron oxide and aluminum oxide (P ₂ O ₅ —B ₂ O ₃ —Al ₂ O ₃ system);
9. A mixture of zinc oxide, phosphorus oxide, silicon oxide, aluminum oxide (ZnO—P ₂ O ₅ —SiO ₂ —Al ₂ O ₃ system);
10. A mixture of zinc oxide, phosphorus oxide and titanium oxide (ZnO—P ₂ O ₅ —TiO ₂ system);
11. A mixture of zinc oxide, boron oxide, silicon oxide and potassium oxide (ZnO—B ₂ O ₃ —SiO ₂ system—K ₂ O system);
12 A mixture of zinc oxide, boron oxide, silicon oxide, potassium oxide, calcium oxide (ZnO—B ₂ O ₃ —SiO ₂ —K ₂ O—CaO system);
13. A mixture of zinc oxide, boron oxide, silicon oxide, potassium oxide, calcium oxide, aluminum oxide (ZnO—B ₂ O ₃ —SiO ₂ —K ₂ O—CaO—Al ₂ O ₃ system);
14 Mixture of bismuth oxide, silicon oxide, potassium oxide, lithium oxide, sodium oxide (Bi ₂ O ₃ —SiO ₂ —K ₂ O—Li ₂ O—Na ₂ O system);
15. A mixture of boron oxide, silicon oxide and aluminum oxide (B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ system);
16. A mixture of boron oxide, silicon oxide, and sodium oxide (B ₂ O ₃ —SiO ₂ —Na ₂ O system);
Of these, environment-friendly lead-free glass is particularly preferable.

  The average particle size of the glass particles (B) is appropriately selected in consideration of the shape of the pattern to be formed, but the 50% by weight average particle size (D50) is preferably 0.2 to 4.0 μm. More preferably, it is 0.5 to 3.8 μm. Moreover, it is preferable that 10 weight% average particle diameter (D10) is 0.05-0.5 micrometer, and 90 weight% average particle diameter (D90) is 10-20 micrometers. When the average particle diameter of the glass particles (B) is in the above range, the exposure light in the exposure step can sufficiently reach the bottom of the photosensitive resin layer, and a high-definition pattern can be obtained.

  The softening point of the glass particles (B) is preferably 350 to 700 ° C, and more preferably 400 to 620 ° C. Glass particles having such a softening point are suitable for forming an electrode constituting a display panel such as an FPD. In the present invention, the softening point of the glass particles (B) is a value measured by DSC measurement under the measurement conditions in Examples described later.

  When the softening point of the glass particles (B) is below the above range, the glass particles may melt at the stage where the organic substance such as the specific aromatic resin (C) is not completely decomposed and removed in the pattern firing step. For this reason, a part of organic substance remains in the formed baking pattern, and there exists a tendency for the electrical resistivity of the formed electrode to rise as a result. On the other hand, when the softening point of the glass particles (B) exceeds the above range, the pattern needs to be baked at a temperature higher than the softening point, and therefore, distortion or the like is likely to occur in a substrate such as a glass substrate.

  The glass particles (B) are pulverized to a predetermined average particle diameter after mixing, melting and solidifying the raw material oxide so as to have a predetermined composition and softening point using a conventionally known method and apparatus. Can be obtained. Moreover, the shape of glass particle (B) is not specifically limited, such as an indefinite shape.

  Examples of the pulverization method include a wet pulverization method such as a medium stirring mill, a colloid mill, and a wet ball mill; a dry pulverization method such as a jet mill, a dry ball mill, and a roll crusher. A plurality of pulverization methods may be used in combination. Moreover, you may perform a classification process in order to adjust the average particle diameter of the powder obtained by grind | pulverizing. As the classification process, a wind classifier or a sieving device can be used.

  The conductive particles (A) and the glass particles (B) are contained in a total amount of preferably 35 to 75% by weight with respect to the entire photosensitive composition. When the total content of the conductive particles (A) and the glass powder (B) is within the above range, oxidation of the conductive particles (A) can be prevented in the firing step, and a low-resistance and high-definition pattern can be formed. Can be manufactured.

  In the photosensitive composition of the present invention, the glass particles (B) are preferably 0.5 to 40 parts by weight, more preferably 5 to 35 parts by weight with respect to 100 parts by weight of the conductive particles (A). Included in range.

<< Specific aromatic resin (C) >>
In the present invention, a specific aromatic resin (C), which is a compound obtained by reacting an aromatic epoxy resin with an unsaturated carboxylic acid and a carboxylic acid anhydride, is used.

  As the aromatic epoxy resin, a compound obtained by reacting at least one polyphenol compound selected from bisphenol A, bisphenol F, 4,4′-dihydroxybiphenyl, phenol novolak and cresol novolak with epichlorohydrin is preferable. Used. Specific examples of the aromatic epoxy resin thus obtained include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin. It is done.

As a reaction ratio of the polyphenol compound and epichlorohydrin, epichlorohydrin is usually 1.4 to 20 mol with respect to 1 mol of the polyphenol compound.
Examples of the bisphenol A type epoxy resin, bisphenol F type epoxy resin, and biphenyl type epoxy resin include resins represented by the following formulas.

式中、Ｒはそれぞれ独立に水素原子またはメチル基を示し、ａは０または１を示し、ｎは０〜２００の整数、好ましくは２〜１００の整数を示す。

In the formula, each R independently represents a hydrogen atom or a methyl group, a represents 0 or 1, and n represents an integer of 0 to 200, preferably an integer of 2 to 100.

  The epoxy equivalent of the aromatic epoxy resin is usually 150 to 1200 g / equivalent. The polystyrene equivalent weight average molecular weight (Mw) of the aromatic epoxy resin is not particularly limited, but is usually 500 to 50,000.

  As the unsaturated carboxylic acid, it is preferable to use at least one selected from acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid and cinnamic acid.

  Examples of the carboxylic acid anhydride include saturated carboxylic acid anhydrides and unsaturated carboxylic acid anhydrides, and unsaturated carboxylic acid anhydrides are particularly preferable. The unsaturated carboxylic acid anhydride is preferably at least one selected from maleic anhydride, itaconic anhydride, citraconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, and pyromellitic anhydride. .

  The specific aromatic resin (C) is a compound obtained by reacting an aromatic epoxy resin with an unsaturated carboxylic acid and a carboxylic acid anhydride; however, the aromatic epoxy resin is reacted with an unsaturated carboxylic acid. A compound obtained by further reacting the adduct obtained above with a carboxylic acid anhydride is preferred.

  In particular, among the specific aromatic resins (C), compounds obtained by reacting an aromatic epoxy resin with an unsaturated carboxylic acid and an unsaturated carboxylic anhydride are preferred; an aromatic epoxy resin with an unsaturated carboxylic acid. A compound obtained by further reacting an unsaturated carboxylic acid anhydride with an adduct obtained by reacting an acid is particularly preferred.

The proportion of the unsaturated carboxylic acid reacted with the aromatic epoxy resin is usually 0.9 to 1.5 equivalents per equivalent of epoxy group of the aromatic epoxy resin.
The ratio of the carboxylic anhydride to react with the aromatic epoxy resin is usually 0.5 to 1 equivalent per equivalent of epoxy group of the aromatic epoxy resin. In addition, when the carboxylic acid anhydride is further reacted with the adduct obtained by reacting the unsaturated carboxylic acid with the aromatic epoxy resin, the amount of the carboxylic acid anhydride used is the amount of the aromatic epoxy before the reaction. What is necessary is just to set it as the said range per 1 equivalent of epoxy groups of resin.

  The addition reaction may be performed according to a conventionally known method. When the unsaturated carboxylic acid is reacted with the aromatic epoxy resin, for example, a solvent such as propylene glycol monomethyl ether acetate, a thermal polymerization inhibitor such as 2-methylhydroquinone, or a reaction catalyst such as triphenylphosphine is used. Can do. Moreover, when making a carboxylic anhydride react with the obtained adduct, the said solvent and the said thermal polymerization inhibitor can be used, for example.

Specific aromatic resin (C) may be used individually by 1 type, and may use 2 or more types together.
In the photosensitive composition of the present invention, the specific aromatic resin (C) is preferably in the range of 20 to 150 parts by weight, more preferably 30 to 120 parts by weight with respect to 100 parts by weight of the conductive particles (A). Included. When the content of the specific aromatic resin (C) is in the above range, it is preferable from the viewpoint of pattern formation and the like.

  The photosensitive composition of the present invention preferably comprises 5 to 90% by weight of a photosensitive resin component and 95 to 10% by weight of inorganic particles; 25 to 65% by weight of the photosensitive resin component and 75 to More preferably, it comprises 35% by weight of inorganic particles. In the present invention, the inorganic particles refer to conductive particles (A), glass particles (B), and the like; the photosensitive resin component refers to a component obtained by removing the inorganic particles from the photosensitive composition.

  The photosensitive resin component includes a specific aromatic resin (C), an ethylenically unsaturated group-containing compound (D), and a photopolymerization initiator (E), and other additives described below (however, inorganic System pigments may be included in the inorganic particles).

<< ethylenically unsaturated group-containing compound (D) >>
As the ethylenically unsaturated group-containing compound (D), a compound having an ethylenically unsaturated group and capable of undergoing radical polymerization reaction with a photopolymerization initiator (E) described later (however, a specific aromatic resin (C) is used) However, the (meth) acrylate compound is generally used.

Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and sec-butyl (meth) acrylate. , Sec-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) Acrylate, butoxytriethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Rate, glycerol (meth) acrylate, glycidyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, isodexyl (meta ) 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, trifluoro Chill (meth) acrylate, aminoethyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, thiophenol (Meth) acrylates such as (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, Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polypropylene glycol (propylene oxide modified) (n≈7) di (meth) acrylate Di (meth) acrylates such as triglycerol di (meth) acrylate;
Pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane (ethylene oxide modified) tri (meth) acrylate, trimethylolpropane (propylene oxide modified) tri (meth) acrylate, benzyl mercaptan tri (meta) ) Trifunctional or higher functional (meth) acrylates such as acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate;
Among the hydrogen atoms bonded to the aromatic ring of the above compound, there may be mentioned monomers in which 1 to 5 are substituted with chlorine atoms or bromine atoms.

An ethylenically unsaturated group containing compound (D) may be used individually by 1 type, and may use 2 or more types together.
In the photosensitive composition of the present invention, the ethylenically unsaturated group-containing compound (D) is preferably 5 parts by weight or more with respect to 100 parts by weight of the conductive particles (A) from the viewpoint of sensitivity to exposure light. Preferably it is contained in the range of 10 to 30 parts by weight. When content of an ethylenically unsaturated group containing compound (D) exceeds the said range, the shape of a baking pattern may deteriorate.

<< Photopolymerization initiator (E) >>
As photopolymerization initiator (E), benzophenone, methyl o-benzoylbenzoate, 4,4′-bis (dimethylamino) 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, 4-azidobenzalacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 2,4 -Diethylthioxanthone, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, methyleneanthrone, dibenzosuberone, 2,6-bis ( p-azidobenzylidene) cyclohexanone, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, Michler's ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2′-dimethoxy-1,2 -Diphenylethane 1-one, camphorquinone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl- Carbonyl compounds such as propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime;
Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenyl Acylphosphine oxide compounds such as phosphine oxide;
Benzyldimethylketanol, benzylmethoxyethyl acetal, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, tetrabromination Examples include carbon, tribromophenyl sulfone, benzoin peroxide, and a combination of a photoreducing dye such as eosin or methylene blue and a reducing agent such as ascorbic acid or triethanolamine. These photoinitiators (E) may be used individually by 1 type, and may use 2 or more types together.

  In addition to the photopolymerization initiator (E), a sensitizer may be used to improve the exposure sensitivity of the photosensitive resin layer. 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, 4,4'-bis ( Dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dimethylamino) chalcone, 4,4′-bis (diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p -Dimethylaminobenzylidene indanone, -(P-dimethylaminophenylvinylene) -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 Examples include -5-benzoylthiotetrazole and 1-phenyl-5-ethoxycarbonylthiotetrazole. The said sensitizer may be used individually by 1 type, and may use 2 or more types together. Some sensitizers also act as photopolymerization initiators.

  In the photosensitive composition of the present invention, the photopolymerization initiator (E) (when the sensitizer is also used, the total of the photopolymerization initiator (E) and the sensitizer) is an ethylenically unsaturated group-containing compound (D ) It is preferably contained in the range of 1 to 50 parts by weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight. When content of a photoinitiator (E) exceeds the said range, the shape of a baking pattern may deteriorate.

《Other additives》
In addition to the above components, the photosensitive composition of the present invention includes an ultraviolet absorber, a polymerization inhibitor, an antioxidant, an organic solvent, an adhesion assistant, a dissolution accelerator, a sensitizer, a dispersant, a thickener, Other additives such as plasticizers, leveling agents and suspending agents may be included.

<Ultraviolet absorber>
You may mix | blend a ultraviolet absorber with the photosensitive composition of this invention. By blending a compound having a high ultraviolet absorption effect, a pattern with 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.

  Specific examples of ultraviolet absorbers include azo dyes, amino ketone dyes, xanthene dyes, quinoline dyes, amino ketone dyes, anthraquinone dyes, benzophenone dyes, diphenyl cyanoacrylate dyes, triazine dyes, p-amino. Organic dyes such as benzoic acid dyes; inorganic pigments such as zinc oxide, titanium oxide, and cerium oxide. Among these, inorganic pigments such as zinc oxide, titanium oxide, and cerium oxide are more preferable from the viewpoint of FPD reliability.

  When using an ultraviolet absorber in the photosensitive composition of this invention, Preferably an ultraviolet absorber is 0.001-5 weight part with respect to 100 weight part of glass particles (B), More preferably, it is 0.01-1. Included in the range of parts by weight. If the content of the ultraviolet absorber is below the above range, the effect of blending the ultraviolet absorber may not be obtained. If the content of the UV absorber exceeds the above range, the effect of blending the UV absorber is great, and exposure light does not reach the bottom of the photosensitive resin layer, making it impossible to form a pattern and maintaining the film strength. Sometimes.

<Polymerization inhibitor>
The photosensitive composition of the present invention may contain a polymerization inhibitor in order to improve the thermal stability during storage. As the polymerization inhibitor, hydroquinone, monoesterified hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-tert-butyl-p-methylphenol, chloranil, Examples include pyrogallol. When a polymerization inhibitor is used in the photosensitive composition of the present invention, the polymerization inhibitor is preferably contained in the range of 0.001 to 1% by weight.

<Antioxidant>
In order to prevent oxidation of the specific aromatic resin (C) during storage, an antioxidant may be added to the photosensitive composition of the present invention. Antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, 2,2′-methylene-bis- ( 4-methyl-6-tert-butylphenol), 2,2'-methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4'-butylidene-bis- (3-methyl-6-t- Butylphenol), 1,1,3-tris- (2-methyl-6-tert-butylphenol) butane, 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. When an antioxidant is used in the photosensitive composition of the present invention, the antioxidant is preferably contained in the range of 0.001 to 1% by weight.

<Organic solvent>
The photosensitive composition of the present invention may contain an organic solvent in order to adjust its viscosity. Organic solvents include terpineol, dihydroterpineol, dihydroterpinel acetate, limonene, carbeol, carvinyl acetate, citronellol, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 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, dimethyl sulfoxide, γ-butyrolactone, bromobenzene, chlorobenzene, dibromobenzene, dichloro Robenzen, bromobenzoic acid, chlorobenzoic acid. An organic solvent may be used individually by 1 type, and may use 2 or more types together. When using the organic solvent in the photosensitive composition of this invention, an organic solvent becomes like this. Preferably it is 15 to 40 weight%, More preferably, it is contained in 20 to 30 weight%.

<Adhesion aid>
In the photosensitive composition of the present invention, an adhesion assistant may be blended in order to improve the adhesion between the photosensitive resin layer and a substrate such as a glass substrate. As the adhesion assistant, a silane compound is preferably used.

  Examples of silane compounds include n-propyldimethylmethoxysilane, n-butyldimethylmethoxysilane, n-decyldimethylmethoxysilane, n-hexadecyldimethylmethoxysilane, n-icosanedimethylmethoxysilane, n-propyldiethylmethoxysilane, n -Butyldiethylmethoxysilane, n-decyldiethylmethoxysilane, n-hexadecyldiethylmethoxysilane, n-icosanediethylmethoxysilane, n-butyldipropylmethoxysilane, n-decyldipropylmethoxysilane, n-hexadecyldi Propylmethoxysilane, n-icosanedipropylmethoxysilane, n-propyldimethylethoxysilane, n-butyldimethylethoxysilane, n-decyldimethylethoxysilane, n-hexadecyldimethyleth Sisilane, n-icosanedimethylethoxysilane, n-propyldiethylethoxysilane, n-butyldiethylethoxysilane, n-decyldiethylethoxysilane, n-hexadecyldiethylethoxysilane, n-icosanediethylethoxysilane, n-butyl Dipropylethoxysilane, n-decyldipropylethoxysilane, n-hexadecyldipropylethoxysilane, n-icosanedipropylethoxysilane, n-propyldimethylpropoxysilane, n-butyldimethylpropoxysilane, n-decyldimethylpropoxysilane N-hexadecyldimethylpropoxysilane, n-icosanedimethylpropoxysilane, n-propyldiethylpropoxysilane, n-butyldiethylpropoxysilane, n-decyldiethylpro Xylsilane, n-hexadecyldiethylpropoxysilane, n-icosanediethylpropoxysilane, n-butyldipropylpropoxysilane, n-decyldipropylpropoxysilane, n-hexadecyldipropylpropoxysilane, n-icosanedipropylpropoxysilane N-propylmethyldimethoxysilane, n-butylmethyldimethoxysilane, n-decylmethyldimethoxysilane, n-hexadecylmethyldimethoxysilane, n-icosanemethyldimethoxysilane, n-propylethyldimethoxysilane, n-butylethyldimethoxy Silane, n-decylethyldimethoxysilane, n-hexadecylethyldimethoxysilane, n-icosaneethyldimethoxysilane, n-butylpropyldimethoxysilane, n-decylpropyl Dimethoxysilane, n-hexadecylpropyldimethoxysilane, n-icosanepropyldimethoxysilane, n-propylmethyldiethoxysilane, n-butylmethyldiethoxysilane, n-decylmethyldiethoxysilane, n-hexadecylmethyldiethoxy Silane, n-icosanemethyldiethoxysilane, n-propylethyldiethoxysilane, n-butylethyldiethoxysilane, n-decylethyldiethoxysilane, n-hexadecylethyldiethoxysilane, n-icosaneethyldi Ethoxysilane, n-butylpropyldiethoxysilane, n-decylpropyldiethoxysilane, n-hexadecylpropyldiethoxysilane, n-icosanepropyldiethoxysilane, n-propylmethyldipropoxysilane, n-butylmethyldi Lopoxysilane, n-decylmethyldipropoxysilane, n-hexadecylmethyldipropoxysilane, n-icosanemethyldipropoxysilane, n-propylethyldipropoxysilane, n-butylethyldipropoxysilane, n-decylethyldipropoxy Silane, n-hexadecylethyldipropoxysilane, n-icosaneethyldipropoxysilane, n-butylpropyldipropoxysilane, n-decylpropyldipropoxysilane, n-hexadecylpropyldipropoxysilane, n-icosampropyl Dipropoxysilane, n-propyltrimethoxysilane, n-butyltrimethoxysilane, n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-icosanetrimethoxysilane, n-propyltriethoxy Silane, n-butyltriethoxysilane, n-decyltriethoxysilane, n-hexadecyltriethoxysilane, n-icosanetriethoxysilane, n-propyltripropoxysilane, n-butyltripropoxysilane, n-decyltripropoxy Silane, n-hexadecyltripropoxysilane, n-icosanetripropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) ) 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3 4 -Epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine , N, N′-bis- [3- (trimethoxysilyl) propyl] ethylenediamine and the like. These silane compounds may be used alone or in combination of two or more.

  In the case where an adhesion assistant is used in the photosensitive composition of the present invention, the adhesion assistant is preferably 0.05 to 15 parts by weight, more preferably 0.1 parts by weight with respect to 100 parts by weight of the specific aromatic resin (C). It is contained in the range of 1 to 10 parts by weight.

<Dissolution accelerator>
In the photosensitive composition of the present invention, a dissolution accelerator may be blended for the purpose of exhibiting sufficient solubility in a developer described later. As the dissolution accelerator, a surfactant is preferably used. Examples of such surfactants include fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, and fatty acids.

  Commercially available fluorinated surfactants include “BM-1000” and “BM-1100” manufactured by BM CHIMIE; “Megafac F142D”, “Same F172” manufactured by Dainippon Ink & Chemicals, Inc., “ "F173", "F183"; "Florard FC-135", "FC-170C", "FC-430", "FC-431" manufactured by Sumitomo 3M Ltd .; manufactured by Asahi Glass Co., Ltd. “Surflon S-112”, “S-113”, “S-131”, “S-141”, “S-145”, “S-382”, “SC-101”, “ SC-102 ”,“ SC-103 ”,“ SC-104 ”,“ SC-105 ”,“ SC-106 ”, and the like.

  Examples of commercially available silicone surfactants include “SH-28PA”, “SH-190”, “SH-193”, “SZ-6032”, “SF-” manufactured by Toray Dow Corning Silicone Co., Ltd. 8428 ”,“ DC-57 ”,“ DC-190 ”;“ KP341 ”manufactured by Shin-Etsu Chemical Co., Ltd .;“ F-top EF301 ”,“ same EF303 ”,“ same EF352 ”manufactured by Shin-Akita Kasei Co., Ltd. Etc.

  Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene distyrenated phenyl ether, polyoxyethylene octylphenyl ether And polyoxyethylene aryl ethers such as polyoxyethylene nonylphenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate.

  Examples of commercially available nonionic surfactants include “Emulgen A-60”, “A-90”, “A-550”, “B-66”, “PP-99” manufactured by Kao Corporation; “(Meth) acrylic acid copolymer polyflow No. 57”, “same No. 90”, and the like manufactured by Chemical Co., Ltd. are included.

  Examples of the fatty acids include butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, palmitoyl acid, margaric acid, stearic acid, oleic acid, vaccenic acid, Examples thereof include linoleic acid, linolenic acid, nonadecanoic acid, arachidic acid, arachidonic acid, behenic acid, lignoselenic acid, nervonic acid, serotic acid, montanic acid, and melicic acid.

  Among the above surfactants, nonionic surfactants are preferred, polyoxyalkylene aryl ethers are more preferred, and particularly the following formula (1), since it is easy to remove the photosensitive resin layer in the unexposed part during development. ) Is preferred.

上記式（１）中、Ｒ¹は炭素数１〜５のアルキル基、好ましくはメチル基であり、ｐは１〜５の整数であり、ｓは１〜５の整数、好ましくは２であり、ｔは１〜１００の整数、好ましくは１０〜２０の整数である。

In the above formula (1), R ¹ is an alkyl group having 1 to 5 carbon atoms, preferably a methyl group, p is an integer from 1 to 5, s is an integer from 1 to 5, preferably 2, t is an integer of 1 to 100, preferably an integer of 10 to 20.

  When a dissolution accelerator is used in the photosensitive composition of the present invention, the dissolution accelerator is preferably 0.001 to 20 parts by weight, more preferably 0.001 parts by weight with respect to 100 parts by weight of the specific aromatic resin (C). It is contained in the range of 01 to 15 parts by weight, particularly preferably 0.1 to 10 parts by weight. When the content of the dissolution accelerator is in the above range, a resin composition having excellent solubility in a developer can be obtained.

<Preparation of photosensitive composition>
The photosensitive composition of the present invention comprises conductive particles (A), glass particles (B), a specific aromatic resin (C), an ethylenically unsaturated group-containing compound (D), and a photopolymerization initiator (E). Then, other additives used as necessary are prepared so as to have a predetermined composition ratio, and then mixed and dispersed homogeneously with a three roll or kneader.

  The photosensitive composition of the present invention may be any composition such as paste, solid, or liquid, but is preferably a paste composition from the viewpoint of moldability and the like. For example, the viscosity of the photosensitive composition prepared as described above is preferably 100 to 500,000 cps (centipoise). In addition, a viscosity can be suitably adjusted with compounding quantities, such as an inorganic particle, a thickener, an organic solvent, a plasticizer, and a suspending agent.

  The photosensitive composition of the present invention is suitably used as a material for forming a display panel member such as an FPD, a member for an advanced mounting material for an electronic component, and a member for a solar cell, particularly a material for forming an electrode for an FPD.

[Pattern formation method]
The pattern forming method of the present invention includes (1) a step of forming a photosensitive resin layer comprising the above photosensitive composition on a substrate (photosensitive resin layer forming step), and (2) a pattern obtained by subjecting the resin layer to exposure treatment. A latent image forming step (exposure step), (3) a step of developing the resin layer on which the pattern latent image is formed to form a pattern (developing step), and (4) baking the pattern. Including a step of performing (firing step).

(1) Photosensitive resin layer formation process In this process, the photosensitive resin layer which consists of the said photosensitive composition is formed on a board | substrate. Examples of the method for forming the photosensitive resin layer include a method in which the photosensitive composition is applied onto a substrate to form a coating film, and the coating film is dried.

  The method for applying the photosensitive composition on the substrate is not particularly limited as long as it is a method capable of efficiently forming a coating film having a large film thickness and excellent uniformity. Examples thereof 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, a coating method using a wire coater, and a screen printing method using a screen printing apparatus.

  What is necessary is just to adjust suitably the drying conditions of a coating film so that the residual ratio of the organic solvent after drying may be within 2 weight%, for example, drying temperature is 50-150 degreeC, and drying time is about 0.5 to 60 minutes. It is.

  The thickness of the photosensitive resin layer formed as described above is preferably 3 to 300 μm, more preferably 5 to 200 μm. In addition, you may form the laminated body which has the photosensitive resin layer of n layer (n shows an integer greater than or equal to 2) by repeating application | coating of a photosensitive composition n times.

(2) Exposure process After forming the photosensitive resin layer on a board | substrate by the said photosensitive resin layer formation process, it exposes using an exposure apparatus. As the exposure is performed by ordinary photolithography, a mask exposure method using an exposure mask can be employed. The exposure pattern of the exposure mask varies depending on the purpose, but is, for example, a stripe or lattice having a width of 10 to 500 μm. Alternatively, a method of directly drawing with a red or blue visible light laser, an Ar ion laser, or the like without using an exposure mask may be used.

  The surface of the photosensitive resin layer is selectively irradiated (exposed) with exposure light such as ultraviolet rays through an exposure mask to form a pattern latent image 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. In addition, when performing exposure of a large area, after applying the photosensitive composition on a substrate such as a glass substrate, the exposure is performed while transporting the substrate, so that a large area can be obtained with an exposure machine having a small exposure area. Can be exposed.

  The exposure light includes visible light, near ultraviolet light, ultraviolet light, electron beam, X-ray, laser light, etc. Among them, ultraviolet light is preferable; the light source of exposure light is a low pressure mercury lamp, a high pressure mercury lamp, or an ultra high pressure. A mercury lamp, a halogen lamp, etc. are mentioned, Among these, an ultrahigh pressure mercury lamp is preferable.

Although the exposure conditions vary depending on the coating thickness, for example, 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.

(3) Development Step After the exposure, the photosensitive resin layer is developed to form a pattern using the difference in solubility between the photosensitive portion and the non-photosensitive portion in the developer. Development methods (eg: immersion method, rocking method, shower method, spray method, paddle method, brush method) and development processing conditions (eg: type / composition / concentration of developer, development time, development temperature) are sensitive. What is necessary is just to select and set suitably according to the kind of conductive resin layer.

  As the developer used in the development step, since the specific aromatic resin (C) is present in the photosensitive resin layer, an alkali developer such as an alkaline aqueous solution can be used. Moreover, the organic solvent which can melt | dissolve the organic substance in the photosensitive resin layer can also be used. Water may be added to the organic solvent as long as its dissolving power is not lost.

  The photosensitive resin layer contains inorganic particles such as conductive particles (A) and glass particles (B), and the inorganic particles are uniformly dispersed by the specific aromatic resin (C). For this reason, the inorganic particles are simultaneously removed by dissolving the specific aromatic resin (C) in 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, Potassium borate, aqueous ammonia, tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropyl Piruamin, diisopropylamine, ethanolamine, diethanolamine, triethanolamine.

  The alkali concentration of the alkaline aqueous solution is usually 0.01 to 10% by weight, preferably 0.1 to 5% by weight. If the alkali concentration is too low, the soluble part is not removed, and if the alkali concentration is too high, the pattern part may be peeled off and the insoluble part 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.

(4) Firing step The firing atmosphere varies depending on the type of photosensitive composition and substrate. For example, this step 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.

  As the baking treatment conditions, it is necessary that the organic substance in the remaining portion of the photosensitive resin layer be burned out. Therefore, the baking temperature is usually 300 to 1000 ° C. and the baking time is 10 to 90 minutes. For example, in the case of forming a pattern on a glass substrate, baking is performed by holding at a temperature of 350 to 600 ° C. for 10 to 60 minutes.

  By the pattern forming method of the present invention including these steps, particularly electrodes such as members of display panels such as FPD, members of advanced mounting materials for electronic components, and members of solar cells can be formed. In addition, you may introduce | transduce the heating process of 50-300 degreeC in the said photosensitive resin layer formation, exposure, image development, and each process of baking for the purpose of drying or preliminary reaction.

[Method of manufacturing electrode for FPD]
By the pattern forming method of the present invention including the above steps, an FPD electrode, a circuit pattern of an electronic component, and the like can be manufactured. Such a method for producing an FPD electrode of the present invention is particularly suitable for producing a PDP electrode.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited at all by these Examples. In the examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, unless otherwise specified.

First, a method for measuring and evaluating physical properties will be described.
[Measurement method of 50% by weight average particle diameter (D50)]
The 50% by weight average particle diameter (D50) of the aluminum powder and the glass powder was measured using a laser diffraction particle size distribution analyzer (“SALD-2000J” manufactured by Shimadzu Corporation).

[Measurement method of Mw and Mw / Mn (number average molecular weight)]
Mw and Mw / Mn are values in terms of polystyrene measured by GPC (“HLC-8220GPC” manufactured by Tosoh Corporation). The GPC measurement was performed using “TSK guard column Super HZM-M” manufactured by Tosoh Corporation as a GPC column under the conditions of a tetrahydrofuran (THF) solvent and a measurement temperature of 40 ° C.

[Measurement method of softening point of glass particle (B)]
Glass particles (B) are sealed in a sample holder, and the temperature is increased from 30 ° C. to 700 ° C. at 10 ° C./min in a nitrogen atmosphere using a differential scanning calorimeter (TA Instruments 2920NDSC), and the obtained endotherm is obtained. The temperature of the peak top was taken as the softening point of the glass particles (B).

[Measurement method of electrical resistivity (volume resistivity)]
A photosensitive composition was applied on a glass substrate and baked to form a baked layer having a thickness of 10 μm on the glass substrate. The volume resistivity X (μΩ · cm) of the fired layer formed on the glass substrate under the conditions of a measurement temperature of 25 ° C. and a measurement humidity of 50% using “Resistivity Processor Model Σ-5” manufactured by NPS is shown below. Measured by reference.
A: X <30
B: 30 ≦ X <80
C: 80 ≦ X

[Method for evaluating pattern after firing]
The panel after baking was cut | disconnected, the pattern cut surface was observed with the scanning electron microscope (Hitachi Ltd. "S4200"), the width | variety and height of the pattern were measured, and each was evaluated on the following reference | standard. The desired standard is a pattern width of 50 μm, a height of 10 μm, and an interval of 100 μm.
○: Within ± 5% of desired standard.
X: Those within ± 20% exceeding ± 5% from the desired standard.

[Synthesis Example 1] Specific aromatic resin (C1)
In a 2 L flask equipped with a stirrer and a reflux tube, bisphenol A type epoxy resin (EP-1004 manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent: 875 to 975 g / equivalent, Mw: 1650) as an aromatic epoxy resin 900 g, 72.3 g of acrylic acid (molecular weight: 72.06) as unsaturated carboxylic acid, 159.1 g of propylene glycol monomethyl ether acetate (hereinafter also referred to as “PGMEA”), and 2-methylhydroquinone as thermal polymerization inhibitor. 0.32 g and 1.9 g of triphenylphosphine as a reaction catalyst were charged and reacted at a temperature of 98 ° C. until the acid value of the reaction solution reached 2 mg · KOH / g or less. Next, 114 g of tetrahydrophthalic anhydride (molecular weight: 152.15) as a carboxylic acid anhydride, 190.9 g of PGMEA, and 0.50 g of 2-methylhydroquinone were added to this reaction solution and reacted at a temperature of 95 ° C. for 5 hours. A resin solution containing 65% by weight of the specific aromatic resin (C1) was obtained.

[Synthesis Example 2] Specific aromatic resin (C2)
In Synthesis Example 1, the aromatic epoxy resin is a bisphenol F type epoxy resin (EP-4005P manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent: 1070 g / equivalent) 1000 g, the amount of acrylic acid used is 72.3 g, tetrahydrophthalic anhydride A resin solution containing the specific aromatic resin (C2) was obtained in the same manner as in Synthesis Example 1 except that the amount of acid used was 114 g.

[Synthesis Example 3] Specific aromatic resin (C3)
In Synthesis Example 1, the aromatic epoxy resin is biphenyl type epoxy resin (NC-3000 manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 276 g / equivalent) 280 g, the amount of acrylic acid used is 72.3 g, tetrahydrophthalic anhydride A resin solution containing the specific aromatic resin (C3) was obtained in the same manner as in Synthesis Example 1 except that the amount used was 114 g.

[Synthesis Example 4] Polymer (C4)
15 parts methacrylic acid as raw material monomer, 10 parts benzyl methacrylate, 40 parts n-butyl methacrylate and 35 parts 2-hydroxyethyl methacrylate; 1 part azobisisobutyronitrile as radical polymerization initiator; pentaerythritol tetrakis (as chain transfer agent) 5 parts of 3-mercaptopropionic acid (manufactured by Sakai Chemical Industry Co., Ltd.) were charged into an autoclave equipped with a stirrer, and stirred in 150 parts of terpineol in a nitrogen atmosphere until uniform.

  Next, the polymerization was carried out at 80 ° C. for 4 hours, and further the polymerization reaction was continued at 100 ° C. for 1 hour, followed by cooling to room temperature to obtain a polymer (C4) having an SH group. The polymerization rate of the polymer (C4) was 98%, and the Mw of the polymer (C4) was 25000.

[Synthesis Example 5] Polymer (C5)
15 parts of methacrylic acid as raw material monomer, 30 parts of 2-ethylhexyl methacrylate, 40 parts of n-butyl methacrylate and 15 parts of 2-ethoxyethyl methacrylate; 1 part of azobisisobutyronitrile as a radical polymerization initiator; pentaerythritol as a chain transfer agent 5 parts of tetrakis (3-mercaptopropionic acid) (manufactured by Sakai Chemical Industry Co., Ltd.) were charged into an autoclave equipped with a stirrer and stirred in 150 parts of terpineol in a nitrogen atmosphere until uniform.

  Next, the polymerization was carried out at 80 ° C. for 4 hours, and further the polymerization reaction was continued at 100 ° C. for 1 hour, followed by cooling to room temperature to obtain a polymer (C5) having an SH group. The polymerization rate of the polymer (C5) was 98%, and the Mw of the polymer (C5) was 25000.

[Example 1]
100 parts of spherical aluminum powder (D50 = 2.0 μm) as conductive particles (A), B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ glass powder (D50 = 1.0 μm, softening point) as glass powder (B) = 510 ° C) 15 parts, specific aromatic resin (C) as specific aromatic resin (C1) 30 parts, ethylenically unsaturated group-containing compound (D) as polypropylene glycol (propylene oxide modified) (n≈7) 10 parts diacrylate, 2 parts 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one as photopolymerization initiator (E), 2,4-diethylthioxanthone as sensitizer One part was kneaded with a kneader to prepare a photosensitive composition. Using this photosensitive composition, the electrical resistivity was measured according to the above [Method for measuring electrical resistivity]. The evaluation results are shown in Table 1.

  Using a 325 mesh screen, the photosensitive composition is printed on a panel made of a glass substrate (150 mm × 150 mm × 2.8 mm) in a solid size of 100 mm square, held at 100 ° C. for 10 minutes and dried. Then, a photosensitive resin layer was formed.

Next, using a negative chrome mask (pattern width 50 μm, pattern interval 100 μm), the photosensitive resin layer was exposed to ultraviolet light from the upper surface with an ultrahigh pressure mercury lamp with an output of 25 mW / cm ² . The exposure amount was 1000 mJ / cm ² .

  Next, the exposed resin layer was developed by applying a 0.5% aqueous sodium carbonate solution maintained at 23 ° C. for 60 seconds in a shower. Then, it washed with water using shower spray, the part which is not photocured was removed, and the grid | lattice-like hardening pattern was formed on the panel.

  Next, the obtained cured pattern was baked at 580 ° C. for 30 minutes to form an electrode pattern. The electrode pattern after firing was evaluated according to the above [Method for evaluating pattern after firing]. The evaluation results are shown in Table 1.

[Examples 2 to 11, Comparative Examples 1 to 4]
In Example 1, an electrode pattern was formed in the same manner as in Example 1 except that a photosensitive composition was prepared with the composition shown in Table 1. The evaluation results are shown in Table 1.

101 glass substrate 102 glass substrate 103 back partition 104 transparent electrode 105 bus electrode 106 address electrode 107 phosphor 108 dielectric layer 109 dielectric layer 110 protective layer 111 front partition 201 glass substrate 202 glass substrate 203 insulating layer 204 transparent electrode 205 emitter 206 Cathode electrode 207 Phosphor 208 Gate 209 Spacer

Claims (9)

(A) conductive particles,
(B) glass particles,
(C) a compound obtained by reacting an aromatic epoxy resin with an unsaturated carboxylic acid and a carboxylic anhydride,
A photosensitive composition comprising (D) an ethylenically unsaturated group-containing compound and (E) a photopolymerization initiator.   In the component (C), the aromatic epoxy resin reacts epichlorohydrin with at least one polyphenol compound selected from bisphenol A, bisphenol F, 4,4′-dihydroxybiphenyl, phenol novolac and cresol novolac. The photosensitive composition according to claim 1, wherein the photosensitive composition is obtained by the following steps.   In the component (C), the unsaturated carboxylic acid is at least one selected from acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid and cinnamic acid. The photosensitive composition of Claim 1 or 2 characterized by these.   In the component (C), the carboxylic acid anhydride is at least one selected from maleic anhydride, itaconic anhydride, citraconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, and pyromellitic anhydride. The photosensitive composition as described in any one of Claims 1-3 characterized by the above-mentioned.   The said electroconductive particle (A) is at least 1 sort (s) of metal type powder selected from the powder which consists of aluminum powder, aluminum alloy powder, and an aluminum complex, As described in any one of Claims 1-4 characterized by the above-mentioned. The photosensitive composition as described.   The conductive particles (A) and the glass particles (B) are contained in a total amount of 35 to 75% by weight with respect to the entire photosensitive composition. The photosensitive composition as described in one term.   It is a forming material of the electrode for flat panel displays, The photosensitive composition as described in any one of Claims 1-6 characterized by the above-mentioned.   (1) The process of forming the photosensitive resin layer which consists of a photosensitive composition as described in any one of Claims 1-7 on a board | substrate, (2) The said resin layer is exposed and the latent image of a pattern is formed. A pattern forming method, comprising: (3) a step of developing the resin layer on which a latent image of the pattern is formed to form a pattern; and (4) a step of baking the pattern. .   An electrode is manufactured by the pattern formation method of Claim 8, The manufacturing method of the electrode for flat panel displays characterized by the above-mentioned.

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