JP2011065166A - Photosensitive paste composition and pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive paste composition that allows a pattern of high precision to be formed at low cost and has small thickness and high adhesive strength to a ceramic, silicon and glass substrate. <P>SOLUTION: The photosensitive paste composition includes: an aluminum powder (A) having a 50 wt.% particle diameter (D50) of 2.0-20.0 μm and including a fatty acid; an alkali-soluble resin (C); a multifunctional (meth)acrylate (D); and a photopolymerization initiator (E). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photosensitive paste composition and a pattern forming method. More specifically, it is suitable for use in forming highly sensitive and accurate patterns in the manufacture of circuit boards having electrodes used for display panels such as flat panel displays, advanced mounting materials for electronic components, and solar cell materials. The present invention relates to a photosensitive paste composition that can be used and a pattern forming method using the composition.

  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 “PED”) and field emission displays (hereinafter also referred to as “FED”) such as plasma display panels (hereinafter also referred to as “PED”). It is also called “FPD”).

  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. 107 is a fluorescent material held in the cell, 108 is a dielectric layer formed on the surface of the glass substrate 101 so as to cover the transparent electrode 104 and the bus electrode 105, and 109 is used to cover the address electrode 106. A dielectric layer formed on the surface of the glass substrate 102, and 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 recent years, FPDs have been increased in size and definition, and accordingly, improvement of pattern processing technology is demanded. However, with the increase in size and definition of the panel, 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, pattern formation by photolithography is used.

  In the production of the electrode by the photolithography method, a large-sized and high-definition pattern, which cannot be dealt with by the screen printing method, can be formed by using the photosensitive silver paste method.

  However, since silver is a noble metal, it is expensive, and 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 easily occurs in a high-temperature and high-humidity environment, and sulfide is generated on the silver surface.

Furthermore, due to the recent demand for cost, there is a demand for an inexpensive inorganic particle-containing photosensitive resin material and a material capable of high-definition pattern processing.
The present invention is intended to solve the problems associated with the prior art as described above, can form a low-cost, high-precision pattern, and has a thin film adhesion strength to ceramic, silicon, and glass substrates. It aims at providing the photosensitive paste composition with high. Another object of the present invention is to provide a pattern forming method using the photosensitive paste composition.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention relates to the following [1] to [7].

  [1] Aluminum powder (A), alkali-soluble resin (C), polyfunctional (meth) acrylate (D) having a 50% by weight particle size (D50) of 2.0 to 20.0 μm and containing fatty acids And a photopolymerization initiator (E).

[2] The photosensitive paste composition as described in [1] above, wherein the content of the aluminum powder (A) is 15 to 70% by weight with respect to the entire photosensitive paste composition.
[3] The alkali-soluble resin (C) is at least one alkali-soluble functional group-containing monomer selected from carboxyl group-containing monomers, hydroxyl group-containing monomers, and phenolic hydroxyl group-containing monomers in all the structural units ( The photosensitive paste composition as described in [1] or [2] above, which is a resin containing 5 to 90% by weight of a structural unit derived from C1).

[4] The photosensitive paste composition according to any one of [1] to [3], wherein the acid value of the alkali-soluble resin (C) is 20 to 200 mgKOH / g.
[5] The glass powder (B) having a 50% by weight particle diameter (D50) of 0.2 to 4.0 μm is further contained, as described in any one of the above [1] to [4] A photosensitive paste composition.

  [6] The glass powder (B) contains glass powder having a softening point of 350 to 700 ° C. in a proportion of 0.5 to 15% by weight with respect to the entire photosensitive paste composition. The photosensitive paste composition as described in [5] above.

  [7] A step of forming a photosensitive paste layer comprising the photosensitive paste composition according to any one of [1] to [6] on a substrate, and exposing the paste layer to a latent image of a pattern A pattern forming method comprising: a step of forming a paste layer, a step of developing the paste layer to form a pattern, and a step of baking the pattern in this order.

  The photosensitive paste composition of the present invention can form a low-priced and high-definition pattern, forms a member constituting an FPD wiring, forms a member of an advanced mounting material for an electronic component, and a member for a solar cell It can be used suitably for formation of.

It is a schematic diagram which shows the cross-sectional shape of an alternating current type plasma display panel. It is a schematic diagram which shows the cross-sectional shape of a general field emission display.

  Hereinafter, the photosensitive paste composition and the pattern forming method of the present invention will be described in detail. Hereinafter, the layer before exposure, which is formed using the photosensitive paste composition, is also referred to as “photosensitive paste layer”.

[Photosensitive paste composition]
The photosensitive paste composition of this invention contains the aluminum powder (A) demonstrated below, alkali-soluble resin (C), polyfunctional (meth) acrylate (D), and a photoinitiator (E). Moreover, you may mix | blend glass powder (B) and another additive with the said photosensitive paste composition.

<Aluminum powder (A)>
The aluminum powder (A) used in the present invention has a 50% by weight particle diameter (D50) of 2.0 to 20.0 μm. Furthermore, it is preferable that a 50 weight% particle diameter is 5.0-15.0 micrometers. When the 50% by weight particle diameter of the aluminum powder (A) is in the above range, light at the time of ultraviolet irradiation sufficiently reaches the bottom of the coating film, and a high-definition pattern can be obtained.

  As aluminum powder (A), when forming the "electrode" which comprises FPD, for example, at least 1 sort (s) of metal powder selected from aluminum powder and its compound can be mentioned. More preferable examples include at least one metal powder selected from an aluminum powder and a compound thereof in which a fatty acid is included. In addition, although it does not specifically limit about the shape of aluminum powder (A), For example, a spherical or flaky thing can be used.

  Examples of the fatty acid 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, vaccene Examples include acids, linoleic acid, linolenic acid, nonadecanoic acid, arachidic acid, arachidonic acid, behenic acid, lignoselenic acid, nervonic acid, serotic acid, montanic acid, and melicic acid.

  In the present invention, the content of the aluminum powder (A) is usually 15 to 70% by weight, preferably 30 to 70% by weight, and more preferably 35 to 65% by weight with respect to the entire photosensitive paste composition. . When the content of the aluminum powder (A) is in the above range, the conductivity is excellent.

  In the present invention, the aluminum powder (A) contains other metals (for example, Pt, Au, Ag, Cu, Sn, Ni, Fe, Zn, W, Mo and compounds thereof) within 20 wt%. May be.

<Glass powder (B)>
The glass powder (B) preferably used in the present invention can be appropriately selected depending on the use of the sintered body formed by the photosensitive paste composition of the present invention (type of FPD member and electronic component).

  Here, the glass powder contained in the composition for forming the “electrode” constituting the FPD is preferably a glass having a softening point in the range of 350 to 700 ° C., more preferably in the range of 400 to 620 ° C. A powder can be mentioned. If the softening point of the glass powder is less than 350 ° C., the glass powder is not completely decomposed and removed in the baking process of the pattern obtained by exposing and developing the photosensitive paste layer. As a result, the organic material may partially remain in the formed electrode. As a result, the electrode is colored and its light transmittance tends to decrease. On the other hand, when the softening point of the glass powder exceeds 700 ° C., the glass substrate needs to be baked at a temperature higher than 700 ° C., so that the glass substrate is likely to be distorted.

As a specific example of a suitable glass powder (B),
1. A mixture of lead oxide, boron oxide, silicon oxide (PbO—B ₂ O ₃ —SiO ₂ system),
2. A mixture of zinc oxide, boron oxide, silicon oxide (ZnO—B ₂ O ₃ —SiO ₂ system),
3. A mixture of lead oxide, boron oxide, silicon oxide, 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. A mixture of bismuth oxide, boron oxide, silicon oxide (Bi ₂ O ₃ —B ₂ O ₃ —SiO ₂ system),
6). A mixture of zinc oxide, phosphorus oxide, silicon oxide (ZnO—P ₂ O ₅ —SiO ₂ system),
7). A mixture of zinc oxide, boron oxide, potassium oxide (ZnO—B ₂ O ₃ —K ₂ O system),
8). A mixture of phosphorus oxide, boron oxide, 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, titanium oxide (ZnO—P ₂ O ₅ —TiO ₂ system),
11. A mixture of zinc oxide, boron oxide, silicon oxide, 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 A mixture of boron oxide, silicon oxide, and aluminum oxide (based on B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ ),
15. Examples thereof include a mixture of boron oxide, silicon oxide, and sodium oxide (B ₂ O ₃ —SiO ₂ —Na ₂ O system). Among these, lead-free glass considering the environment is particularly preferable.

  When forming an electrode member, for example, the content of the glass powder (B) is usually 0.5 to 35% by weight with respect to the entire photosensitive paste composition. Preferably it is 0.5 to 25 weight%. More preferably, it is 1.0 to 20% by weight. In particular, it is preferable to contain glass powder having a softening point of 350 to 700 ° C. in a proportion of 0.5 to 15% by weight with respect to the entire photosensitive paste composition, and in a proportion of 1.0 to 10% by weight. It is more preferable to contain.

  The average particle size of the glass powder (B) is appropriately selected in consideration of the shape of the pattern to be produced, but the 50 wt% particle size (D50) of the glass powder (B) is 0.2-4. It is preferably 0.0 μm. Further, the 50% by weight particle diameter (D50) is more preferably 0.5 to 3.8 μm. Furthermore, it is preferable that the 10 wt% particle size (D10) is 0.05 to 0.5 µm and the 90 wt% particle size (D90) is 10 to 20 µm. When the average particle diameter of the glass powder (B) is in the above range, light at the time of ultraviolet irradiation can sufficiently reach the bottom of the coating film, and a high-definition pattern can be obtained.

<Alkali-soluble resin (C)>
The alkali-soluble resin (C) used in the present invention is not particularly limited as long as it is alkali-soluble. In the present invention, “alkali-soluble” means a property of being dissolved in an alkaline developer to such an extent that the intended development processing is possible.
As the alkali-soluble resin (C), a copolymer of the following alkali-soluble functional group-containing monomer (C1) and a (meth) acrylic acid derivative (C2) is preferable.

≪Alkali-soluble functional group-containing monomer (C1) ≫
Examples of the alkali-soluble functional group-containing monomer (C1) include (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, and succinic mono (2- (meth) acrylic acid). Leuoxyethyl), 2-methacryloyloxyethylphthalic acid, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2-acryloyloxypropyl tetrahydrophthalate, ω Carboxyl group-containing monomers such as carboxy-polycaprolactone mono (meth) acrylate;
Hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (α-hydroxymethyl) acrylate;
Examples include monomers having an alkali-soluble functional group and an unsaturated bond, such as phenolic hydroxyl group-containing monomers such as o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene.

  Among these monomers, (meth) acrylic acid, 2-methacryloyloxyethylphthalic acid, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2-acryloyl Oxypropyltetrahydrohydrogenphthalate and 2-hydroxyethyl (meth) acrylate are preferred.

  By copolymerizing the alkali-soluble functional group-containing monomer (C1), alkali solubility can be imparted to the resin. The content of the constituent unit derived from the alkali-soluble functional group-containing monomer (C1) is usually 5 to 90% by weight, preferably 10 to 80% by weight, particularly preferably, in all the constituent units of the alkali-soluble resin (C). 15 to 70% by weight.

≪ (Meth) acrylic acid derivative (C2) ≫
The (meth) acrylic acid derivative (C2) is not particularly limited as long as it is a (meth) acrylic acid derivative copolymerizable with the alkali-soluble functional group-containing monomer (C1). For example, methyl (meth) acrylate, ethyl ( (Meth) acrylate, n-butyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Other than the above monomer (C1) such as phenoxyethyl (meth) acrylate, trityl (meth) acrylate, cyclohexyl (meth) acrylate, isoboronyl (meth) acrylate, glycidyl (meth) acrylate, and dicyclopentanyl (meth) acrylate Meth) acrylates and the like.

  In the present invention, instead of (meth) acrylic acid derivative (C2) or in addition to (meth) acrylic acid derivative (C2), for example, styrene, methyl (meth) acrylate, ethyl (meth) acrylate, benzyl A macromonomer having a polymerizable unsaturated group such as a (meth) acryloyl group, an allyl group, or a vinyl group may be used at one chain end of a polymer obtained from (meth) acrylate or the like.

≪Radical polymerization initiator≫
In the copolymerization, it is preferable to use a radical polymerization initiator. As the radical polymerization initiator, a radical polymerization initiator used for polymerization of a vinyl monomer can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutylnitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 1,1′-azobis Azo compounds such as (1-cyclohexanecarbonitrile), dimethyl-2,2′-azobisisobutyrate, 4,4′-azobis (4-cyanovaleric acid); t-butyl peroxybivalate, t- Examples thereof include organic peroxides of peroxyesters such as butyl peroxy 2-ethylhexanoate and cumyl peroxy 2-ethylhexanoate. These radical polymerization initiators may be used alone or in combination of two or more. The usage-amount of these radical polymerization initiators is about 0.1-10 weight part with respect to 100 weight part of all the monomers used for the said copolymerization.

≪Chain transfer agent≫
A chain transfer agent may be used in the copolymerization. Examples of the chain transfer agent include α-methylenestyrene dimer, t-dodecyl mercaptan, pentaerythritol tetrakis (3-mercaptopropionic acid), pentaerythritol tetrakis (3-mercaptobutyrate), and 1,4-bis (3-mercapto). Butyryloxy) butane.

The amount of the chain transfer agent used is usually about 0.1 to 10 parts by weight with respect to 100 parts by weight of all monomers used for the copolymerization.
The weight average molecular weight (hereinafter also referred to as “Mw”) of the alkali-soluble resin (C) is a polystyrene conversion value measured by gel permeation chromatography (GPC), preferably 5,000 to 100,000, more preferably 10,000 to 80000. is there. Mw can be controlled by appropriately selecting conditions such as a copolymerization ratio of the monomer, a chain transfer agent, and a polymerization temperature. When Mw is lower than the above range, film roughness after development is likely to occur, and when Mw exceeds the above range, the solubility of the unexposed portion in the developer may be reduced and resolution may be reduced. .

  The glass transition temperature (Tg) of the alkali-soluble resin (C) is preferably 0 to 120 ° C, more preferably 10 to 100 ° C. When the glass transition temperature is lower than the above range, the coating film tends to be tacky and is difficult to handle. Further, when the glass transition temperature exceeds the above range, the adhesion between the photosensitive paste layer and the glass substrate as a support is deteriorated, and when the transfer film described later is used, the paste layer cannot be transferred. is there. The glass transition temperature can be appropriately adjusted by changing the amounts of the alkali-soluble functional group-containing monomer (C1) and the (meth) acrylic acid derivative (C2).

  The acid value of the alkali-soluble resin (C) is preferably 20 to 200 mgKOH / g, more preferably 30 to 160 mgKOH / g. When the acid value is less than 20 mgKOH / g, it is difficult to quickly remove the unexposed portion after exposure with an alkaline developer, and it tends to be difficult to form a high-definition pattern. On the other hand, when the acid value exceeds 200 mgKOH / g, the portion cured by the exposure light tends to be eroded by the alkaline developer, and it tends to be difficult to form a high-definition pattern.

  In the photosensitive paste composition of the present invention, the photosensitive resin component refers to a portion obtained by removing inorganic particles from the composition, that is, the entire organic component having a photosensitive function. Here, the said inorganic particle points out aluminum powder (A), glass powder (B), etc.

The photosensitive resin component includes an alkali-soluble resin (C), a polyfunctional (meth) acrylate (D), a photopolymerization initiator (E), and further a sensitizer, a sensitizer, and an organic ultraviolet ray. Add additive components such as absorbents, polymerization inhibitors, antioxidants, plasticizers, thickeners, organic solvents, adhesion aids, dissolution promoters, dispersants, anti-settling agents for each component, and leveling agents. Can do.
The photosensitive paste 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.

<Multifunctional (meth) acrylate (D)>
The photosensitive paste composition of the present invention contains a photosensitive component. The photosensitive component is generally classified into a light insolubilizing type and a light solubilizing type.

  Examples of the photo-insoluble type include (i) those containing a photosensitive monomer or oligomer having one or more unsaturated groups in the molecule, (ii) aromatic diazo compounds, aromatic azide compounds, organic halogen compounds, etc. And (iii) so-called diazo resins such as a condensate of diazo amine and formaldehyde.

  Examples of the light solubilizing type include (iv) a complex of a diazo compound with an inorganic acid or an organic acid, a quinone diazo compound, (v) a quinone diazo compound combined with an appropriate polymer binder, such as a phenol resin. Naphthoquinone-1,2-diazide-5-sulfonic acid ester.

  In the present invention, all of the above can be used, but the polyfunctional (meth) acrylate classified as (i) above is an essential component in that it can be easily used by mixing with the inorganic particles. Used as

Specific examples of the polyfunctional (meth) acrylate (D) used in the present invention include allylated cyclohexyl di (meth) acrylate, 2,5-hexanedi (meth) acrylate, and 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, triglycero Di (meth) methacrylate such as distearate (meth) acrylate;
Pentaerythritol tri (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylolpropane PO modified tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol Trifunctional or higher functional (meth) acrylates such as monohydroxypenta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, and benzyl mercaptan (meth) acrylate;
Among the aromatic ring hydrogen atoms in the above compounds, there may be mentioned monomers in which 1 to 5 are substituted with chlorine or bromine atoms. These polyfunctional (meth) acrylates (D) may be used singly or in combination of two or more.

  In the photosensitive paste composition of the present invention, the polyfunctional (meth) acrylate (D) is preferably 10% by weight or more, more preferably 15 to more than the entire photosensitive resin component from the viewpoint of sensitivity to light. Used in an amount of 60% by weight. When content of polyfunctional (meth) acrylate (D) exceeds the said range, the shape of the member for display panels after baking may deteriorate.

  Moreover, within the range which does not impair the objective of this invention, it is styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, chlorinated styrene, brominated styrene, (alpha)-with polyfunctional (meth) acrylate (D). Methylstyrene, chlorinated α-methylstyrene, brominated α-methylstyrene, chloromethylstyrene, hydroxymethylstyrene, carboxymethylstyrene, vinylnaphthalene, vinylanthracene, vinylcarbazole, γ-methacryloxypropyltrimethoxysilane, 1- Vinyl-2-pyrrolidone or the like may be used.

<Photopolymerization initiator (E)>
Examples of the photopolymerization initiator (E) used in the present invention include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamino) benzophenone, 4,4. -Dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methyl Propiophenone, pt-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 2,4-diethyl Oxanthone, benzyldimethylketanol, benzylmethoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methylene Anthrone, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexanone, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2 -(O-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxyca) Rubonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, Michler's ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane-1 -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2'-dimethoxy- 1,2-diphenylethane-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis ( 2,4,6-trimethylbenzoyl) -phenylphosphine oxide, naphthalenesulfonyl chloride Quinolinesulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylformine, camphorquinone, tetrabrominated carbon, tribromophenyl sulfone, peroxy Examples thereof include a combination of benzoin oxide and a photoreductive dye such as eosin or methylene blue and a reducing agent such as ascorbic acid or triethanolamine. A photoinitiator (E) may be used individually by 1 type, or may be used in combination of 2 or more type.

  The content of the photopolymerization initiator (E) is preferably 1 to 50 parts by weight, more preferably 2 to 40 parts by weight with respect to 100 parts by weight of the polyfunctional (meth) acrylate (D). When content of a photoinitiator (E) exceeds the said range, the shape of the member for display panels after baking may deteriorate.

<Ultraviolet absorber>
In the present invention, it is also effective to add an ultraviolet absorber to the photosensitive paste composition. By adding 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.

  Specifically, azo dyes, amino ketone dyes, xanthene dyes, quinoline dyes, amino ketone dyes, anthraquinone dyes, benzophenone dyes, diphenyl cyanoacrylate dyes, triazine dyes, p-aminobenzoic acid dyes Organic pigments such as zinc oxide, titanium oxide, cerium oxide and other inorganic pigments can be used. Among these, for example, when an insulating film is formed using the photosensitive paste composition of the present invention, the organic dye does not remain in the insulating film after firing, which is preferable because the deterioration of the insulating film characteristics can be reduced. From the viewpoint of the reliability of FPD, inorganic pigments such as zinc oxide, titanium oxide, and cerium oxide are more preferable.

  The inorganic pigment can be added in an amount of preferably 0.001 to 5 parts by weight, more preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the glass powder (B). If it is less than 0.001 part by weight, the effect of adding the UV absorber is reduced, and if it exceeds 5 parts by weight, the effect of the UV absorber is so great that light does not reach the lower part of the film, making it impossible to form a pattern and the film strength is increased. Sometimes I can't keep it.

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

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

<Polymerization inhibitor>
A polymerization inhibitor may be added to the photosensitive paste composition of the present invention in order to improve the thermal stability during storage. Examples of the polymerization inhibitor include hydroquinone, monoesterified hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-tert-butyl-p-methylphenol, Examples include chloranil and pyrogallol. The polymerization inhibitor can be added to the photosensitive paste composition in an amount preferably in the range of 0.001 to 1% by weight.

<Antioxidant>
In order to prevent oxidation of the alkali-soluble resin (C) during storage, an antioxidant may be added to the photosensitive paste composition of the present invention. Examples of the antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-4-ethylphenol, 2,2-methylene-bis- (4 -Methyl-6-tert-butylphenol), 2,2-methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4-bis- (3-methyl-6-tert-butylphenol), 1, 1,3-tris- (2-methyl-6-tert-butylphenol), 1,1,3-tris- (2-methyl-4-hydroxy-tert-butylphenyl) butane, bis [3,3-bis- (4-Hydroxy-3-t-butylphenyl) butyric acid] glycol ester, dilauryl thiodipropionate, triphenyl phosphite and the like. The antioxidant can be added to the photosensitive paste composition in an amount preferably in the range of 0.001 to 1% by weight.

<Organic solvent>
An organic solvent may be added to the photosensitive paste composition of the present invention in order to adjust the viscosity of the solution. Examples of the organic solvent 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, dibromobenze , Dichlorobenzene, bromobenzoic acid, chlorobenzoic acid. The said organic solvent may be used individually by 1 type, or 2 or more types may be mixed and used for it.

<Adhesion aid>
An adhesion assistant may be added to the photosensitive paste composition of the present invention in order to improve the adhesion between the photosensitive paste layer and the support. As the adhesion assistant, a silane compound is preferably used. Specific examples of the silane compound include n-propyldimethylmethoxysilane, n-butyldimethylmethoxysilane, n-decyldimethylmethoxysilane, n-hexadecyldimethylmethoxysilane, n-icosanedimethylmethoxysilane, and n-propyldiethylmethoxy. Silane, n-butyldiethylmethoxysilane, n-decyldiethylmethoxysilane, n-hexadecyldiethylmethoxysilane, n-icosanediethylmethoxysilane, n-butyldipropylmethoxysilane, n-decyldipropylmethoxysilane, n- Hexadecyldipropylmethoxysilane, n-icosanedipropylmethoxysilane, n-propyldimethylethoxysilane, n-butyldimethylethoxysilane, n-decyldimethylethoxysilane, n-hexadecyldimethyl Ruethoxysilane, n-icosanedimethylethoxysilane, n-propyldiethylethoxysilane, n-butyldiethylethoxysilane, n-decyldiethylethoxysilane, n-hexadecyldiethylethoxysilane, n-icosanediethylethoxysilane, n -Butyldipropylethoxysilane, n-decyldipropylethoxysilane, n-hexadecyldipropylethoxysilane, n-icosanedipropylethoxysilane, n-propyldimethylpropoxysilane, n-butyldimethylpropoxysilane, n-decyldimethyl Propoxysilane, n-hexadecyldimethylpropoxysilane, n-icosanedimethylpropoxysilane, n-propyldiethylpropoxysilane, n-butyldiethylpropoxysilane, n-decyldie Lupropoxysilane, n-hexadecyldiethylpropoxysilane, n-icosanediethylpropoxysilane, n-butyldipropylpropoxysilane, n-decyldipropylpropoxysilane, n-hexadecyldipropylpropoxysilane, n-icosanedipropyl Propoxysilane, n-propylmethyldimethoxysilane, n-butylmethyldimethoxysilane, n-decylmethyldimethoxysilane, n-hexadecylmethyldimethoxysilane, n-icosanemethyldimethoxysilane, n-propylethyldimethoxysilane, n-butyl Ethyldimethoxysilane, n-decylethyldimethoxysilane, n-hexadecylethyldimethoxysilane, n-icosaneethyldimethoxysilane, n-butylpropyldimethoxysilane, n-decyl Propyldimethoxysilane, n-hexadecylpropyldimethoxysilane, n-icosanepropyldimethoxysilane, n-propylmethyldiethoxysilane, n-butylmethyldiethoxysilane, n-decylmethyldiethoxysilane, n-hexadecylmethyldi Ethoxysilane, n-icosanemethyldiethoxysilane, n-propylethyldiethoxysilane, n-butylethyldiethoxysilane, n-decylethyldiethoxysilane, n-hexadecylethyldiethoxysilane, n-icosaneethyl Diethoxysilane, n-butylpropyldiethoxysilane, n-decylpropyldiethoxysilane, n-hexadecylpropyldiethoxysilane, n-icosanepropyldiethoxysilane, n-propylmethyldipropoxysilane, n-butyl Tildipropoxysilane, n-decylmethyldipropoxysilane, n-hexadecylmethyldipropoxysilane, n-icosanemethyldipropoxysilane, n-propylethyldipropoxysilane, n-butylethyldipropoxysilane, n-decyl Ethyldipropoxysilane, n-hexadecylethyldipropoxysilane, n-icosaneethyldipropoxysilane, n-butylpropyldipropoxysilane, n-decylpropyldipropoxysilane, n-hexadecylpropyldipropoxysilane, n- Icosanpropyl dipropoxysilane, n-propyltrimethoxysilane, n-butyltrimethoxysilane, n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-icosanetrimethoxysilane, n-propylto Ethoxysilane, n-butyltriethoxysilane, n-decyltriethoxysilane, n-hexadecyltriethoxysilane, n-icosanetriethoxysilane, n-propyltripropoxysilane, n-butyltripropoxysilane, n-decyltri Propoxysilane, n-hexadecyltripropoxysilane, n-icosanetripropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-amino Ethyl) 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)- Examples include 1-propanamine, N, N′-bis- [3- (trimethoxysilyl) propyl] ethylenediamine, and the like. These may be used alone or in combination of two or more.

  The content of the adhesion assistant in the photosensitive paste composition is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, with respect to 100 parts by weight of the alkali-soluble resin (C). .

<Dissolution accelerator>
The photosensitive paste composition of the present invention preferably contains a dissolution accelerator 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.

  Examples of the fluorosurfactant include “BM-1000” and “BM-1100” manufactured by BM CHIMIE, “Megafac F142D”, “Same F172”, and “Same F172” manufactured by Dainippon Ink & Chemicals, Inc. "F173", "F183", "Florard FC-135", "FC-170C", "FC-430", "FC-431" manufactured by Sumitomo 3M Ltd., "Asahi Glass Co., Ltd." “Surflon S-112”, “S-113”, “S-131”, “S-141”, “S-145”, “S-382”, “SC-101”, “Same” Commercial products such as “SC-102”, “SC-103”, “SC-104”, “SC-105”, and “SC-106” can be mentioned.

  Examples of the silicone surfactant include “SH-28PA”, “SH-190”, “SH-193”, “SZ-6032”, “SF-8428” manufactured by Toray Dow Corning Silicone Co., Ltd. ”,“ 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. Can be mentioned.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene distyrenated phenyl ether, polyoxyethylene octyl And polyoxyethylene aryl ethers such as phenyl ether and 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”, and “PP-99” manufactured by Kao Corporation. “(Meth) acrylic acid copolymer polyflow No. 57” and “No. 90” manufactured by Kyoeisha Chemical Co., Ltd. can be mentioned.

  Among the above surfactants, nonionic surfactants are preferable, polyoxyethylene aryl ethers are more preferable, and particularly the following formula (1), since it is easy to remove the unexposed photosensitive paste layer 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.

  Examples of the fatty acid 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, vaccene Examples include acids, linoleic acid, linolenic acid, nonadecanoic acid, arachidic acid, arachidonic acid, behenic acid, lignoselenic acid, nervonic acid, serotic acid, montanic acid, and melicic acid.

  The content of the dissolution accelerator in the photosensitive paste composition of the present invention is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (C). Particularly preferred is 0.1 to 10 parts by weight. When the content of the dissolution accelerator is in the above range, a composition having excellent solubility in a developer can be obtained.

<Preparation of photosensitive paste composition>
The photosensitive paste composition of the present invention comprises an aluminum powder (A), an alkali-soluble resin (C), a polyfunctional (meth) acrylate (D), and a photopolymerization initiator (E), and glass used as necessary. The above-mentioned various components such as the powder (B) and the organic solvent are prepared so as to have a predetermined composition ratio, and then mixed and dispersed homogeneously with a three roll or kneader.

  The viscosity of the photosensitive paste composition of the present invention can be adjusted as appropriate depending on the amount of inorganic particles, thickener, organic solvent, plasticizer, precipitation inhibitor and the like, but the range is preferably 100 to 500,000 cps ( Centimeter poise).

[Pattern formation method]
The pattern forming method of the present invention comprises a step of forming a photosensitive paste layer comprising the above photosensitive paste composition on a substrate (photosensitive paste layer forming step), and exposing the photosensitive paste layer to a latent pattern image. And a step of developing the photosensitive paste layer to form a pattern (developing step), and a step of baking the pattern (baking step).

<Photosensitive paste layer forming step>
In this step, a photosensitive paste layer made of the photosensitive paste composition is formed on the substrate. Examples of the method for forming the photosensitive paste layer include a method in which the photosensitive paste composition is applied onto a substrate to form a coating film, and the coating film is dried.

  The method for applying the photosensitive paste 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 (for example, 20 μm or more) 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 less than 2 weight%, for example, is about 0.5 to 60 minutes at the drying temperature of 50-150 degreeC.
The thickness of the photosensitive paste 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 paste layer of n layer (n shows an integer greater than or equal to 2) by repeating application | coating of the photosensitive paste composition n times.

<Exposure process>
After the photosensitive paste layer is formed on the substrate by the photosensitive paste layer forming step, exposure is performed using an exposure apparatus. As the exposure is performed by ordinary photolithography, a mask exposure method using a photomask 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 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.
A surface of the photosensitive paste layer is selectively irradiated (exposed) with radiation such as ultraviolet rays through an exposure mask to form a pattern latent image on the paste layer. As the exposure apparatus, a parallel light exposure machine, a scattered light exposure machine, a stepper exposure machine, a proximity exposure machine, or the like can be used. Moreover, when performing exposure of a large area, after applying a photosensitive paste composition on a substrate such as a glass substrate, exposure is performed while being conveyed, thereby exposing a large area with an exposure machine having a small exposure area. be able to.

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

<Development process>
After the exposure, the photosensitive paste layer is developed to form a pattern using the difference in solubility in the developer between the photosensitive part and the non-photosensitive part. Development methods (eg, dipping method, rocking method, shower method, spray method, paddle method, brush method, etc.) and development processing conditions (eg, developer type / composition / concentration, development time, development temperature, etc.) The selection and setting may be made as appropriate according to the type of the photosensitive paste layer.

  As the developer used in the development step, an organic solvent capable of dissolving the organic components in the photosensitive paste layer can be used. Further, water may be added to the organic solvent as long as its dissolving power is not lost. When a compound having an acidic group such as a carboxyl group is present in the photosensitive paste layer, development can be performed with an alkaline aqueous solution.

  The photosensitive paste layer contains inorganic particles such as aluminum powder (A), preferably glass powder (B), and the inorganic particles are uniformly dispersed by the alkali-soluble resin (C). The inorganic particles are simultaneously removed by dissolving the resin (C) with a developer and washing.

  Examples of the alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate, phosphorus 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, lithium borate, boric acid Sodium, potassium borate, aqueous ammonia, tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Isopropylamine, diisopropylamine, ethanolamine, diethanolamine, triethanolamine.

  The 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.

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

  As the baking treatment conditions, it is necessary that the organic substance in the remaining part of the photosensitive paste layer is 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, a display panel member such as an electrode, a circuit pattern of an electronic component, a wiring pattern of a solar cell member, and the like can be formed. In addition, you may introduce | transduce a 50-300 degreeC heating process for the purpose of drying or a preliminary reaction in each process of the said photosensitive paste layer formation, exposure, image development, and baking.

[Method for manufacturing FPD members]
By the pattern forming method of the present invention including the above steps, an FPD member such as an electrode, a circuit pattern of an electronic component, a wiring pattern of a solar cell member, and the like can be formed. Such a method for producing an FPD member of the present invention is suitable for a method for producing a PDP.

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.

[Method for Measuring Weight Average Molecular Weight (Mw) and Weight Average Molecular Weight (Mw) / Number Average Molecular Weight (Mn) (hereinafter referred to as Mw / Mn)]
Mw and Mw / Mn are values in terms of polystyrene measured by gel permeation chromatography (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.

[Evaluation method of electrical resistance measurement]
The volume resistance [μΩ · cm] is obtained by applying a photosensitive paste composition on a glass substrate and baking it to form a 10 μm-thick film on the glass substrate, and the “Resistivity Processor Model Σ manufactured by NPS” -5 ".

[Method for evaluating pattern after development and baking]
The developed and fired test pieces were cut, the pattern cut surface was observed with a scanning electron microscope (“S4200” manufactured by Hitachi, Ltd.), the pattern width and height were measured, and each was evaluated according to the following criteria. . The desired standard is a pattern width of 50 μm, a height of 10 μm, and an interval of 100 μm.
A: The desired standard.
B: Within ± 5% of desired standard.
C: A value exceeding ± 5% and within ± 10% from a desired standard.
D: More than ± 10% from the desired standard.
−: The pattern cannot be evaluated due to peeling of the pattern.

[Evaluation of pattern adhesion after firing]
Evaluation of adhesion between the pattern and the glass substrate as the support was performed on the test piece after firing as follows. The desired standard is a pattern width of 50 μm, a height of 10 μm, and an interval of 100 μm.

Cello tape (registered trademark: manufactured by Nichiban Co., Ltd.) was thermocompression bonded to the surface of the support constituting the test piece with a heating roller. The pressure bonding conditions were such that the surface temperature of the heating roller was 23 ° C., the roll pressure was 4 kg / cm ² , and the moving speed of the heating roller was 0.5 m / min. As a result, cellophane tape (registered trademark: manufactured by Nichiban Co., Ltd.) was transferred to the surface of the support and brought into close contact. The adhesiveness of the pattern was evaluated by peeling this cello tape (registered trademark: manufactured by Nichiban Co., Ltd.) from the support.
○: No pattern peeling.
X: Pattern peeling occurred.

[Synthesis Example 1]
2-methacryloyloxyethylphthalic acid 45 parts, benzyl methacrylate 55 parts, azobisisobutyronitrile (AIBN) 1 part, pentaerythritol tetrakis (3-mercaptopropionic acid) (manufactured by Sakai Chemical Industry Co., Ltd.) The mixture was charged into an autoclave equipped with a stirrer and stirred in 150 parts of terpineol in a nitrogen atmosphere until uniform.

  Subsequently, after making it superpose | polymerize at 80 degreeC for 4 hours and also continuing a polymerization reaction at 100 degreeC for 1 hour, it cooled to room temperature and obtained alkali-soluble resin (1) which has SH group. The polymerization rate of this alkali-soluble (1) was 98%, and the weight average molecular weight was 20000 (Mw / Mn 1.8).

[Synthesis Example 2]
An alkali-soluble resin (2) was obtained in the same manner as in Synthesis Example 1 except that 5 parts of NOFMER NSD (manufactured by NOF Corporation) was used instead of 5 parts of pentaerythritol tetrakis (3-mercaptopropionic acid). . The polymerization rate of this alkali-soluble resin (2) was 98%, and the weight average molecular weight was 25000 (Mw / Mn 2.2).

[Synthesis Example 3]
25 parts of methacrylic acid, 75 parts of benzyl methacrylate, 1 part of azobisisobutyronitrile (AIBN), 5 parts of NOFMER NSD (manufactured by Nippon Oil & Fats Co., Ltd.) are charged into an autoclave equipped with a stirrer and in 150 parts of terpineol in a nitrogen atmosphere And stirred until uniform.

  Subsequently, after making it superpose | polymerize at 80 degreeC for 4 hours and also continuing a polymerization reaction at 100 degreeC for 1 hour, it cooled to room temperature and obtained alkali-soluble resin (3). The polymerization rate of this alkali-soluble resin (3) was 98%, and the weight average molecular weight was 25000 (Mw / Mn 2.3).

[Synthesis Example 4]
25 parts of methacrylic acid, 75 parts of benzyl methacrylate, 1 part of azobisisobutyronitrile (AIBN), 5 parts of pentaerythritol tetrakis (3-mercaptopropionic acid) (manufactured by Sakai Chemical Industry Co., Ltd.) are charged into an autoclave equipped with a stirrer. The mixture was stirred in 150 parts of terpineol in a nitrogen atmosphere until uniform.

  Subsequently, after making it superpose | polymerize at 80 degreeC for 4 hours and also continuing a polymerization reaction at 100 degreeC for 1 hour, it cooled to room temperature and obtained alkali-soluble resin (4). The polymerization rate of this alkali-soluble resin (4) was 98%, and the weight average molecular weight was 25000 (Mw / Mn 2.3).

[Synthesis Example 5]
25 parts of methacrylic acid, 75 parts of benzyl methacrylate, 1 part of azobisisobutyronitrile (AIBN), 5 parts of pentaerythritol tetrakis (3-mercaptopropionic acid) (manufactured by Sakai Chemical Industry Co., Ltd.) are charged into an autoclave equipped with a stirrer. The mixture was stirred in 150 parts of propylene glycol monomethyl ether under nitrogen atmosphere until uniform.

  Subsequently, after making it superpose | polymerize at 80 degreeC for 4 hours and also continuing a polymerization reaction at 100 degreeC for 1 hour, it cooled to room temperature and obtained alkali-soluble resin (5). The polymerization rate of this alkali-soluble resin (5) was 98%, and the weight average molecular weight was 20000 (Mw / Mn 2.0).

[Preparation of photosensitive resin component]
Photosensitive resin components (1) to (6) having the compositions shown in Table 3 were prepared.

[Example 1]
Aluminum powder A1 (16 g) shown in Table 1, glass powder B1 (2 g) shown in Table 2, and photosensitive resin component (1) (40 g) shown in Table 3 were kneaded with a kneader to prepare a photosensitive paste composition ( Hereinafter also referred to as “photosensitive paste”).

  Using a 325 mesh screen, the above photosensitive paste is printed on a glass substrate, which is a test piece (150 mm × 150 mm × 2.8 mm), in a 100 mm square size, held at 100 ° C. for 10 minutes, and dried. Then, a photosensitive paste layer was formed.

Next, using a negative chrome mask (pattern width 50 μm, pattern interval 100 μm), the photosensitive paste 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 photosensitive paste layer was developed by applying a 0.5% aqueous solution of sodium carbonate maintained at 23 ° C. for 60 seconds in a shower. Then, it washed with water using shower spray, the part which has not been photocured was removed, and the lattice-shaped hardening pattern was formed on the glass substrate. The cured pattern after development was evaluated by the above evaluation method. The results are shown in Table 4.

  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 by the above evaluation method. The results are shown in Table 4.

[Examples 2 to 15]
A photosensitive paste layer, a cured pattern, and an electrode pattern were sequentially formed on a glass substrate in the same manner as in Example 1 except that a photosensitive paste was prepared using the aluminum powder, glass powder, and photosensitive resin component shown in Table 4. Formed. Next, the cured pattern and the electrode pattern were evaluated by the above evaluation method. The results are shown in Table 4. In any of Examples 1 to 15, the film thickness of the photosensitive paste layer was in the range of 10 μm ± 1 μm.

[Example 16]
A photosensitive paste layer, a cured pattern, and an electrode pattern were sequentially formed on a glass substrate in the same manner as in Example 1 except that a photosensitive paste was prepared using the aluminum powder, glass powder, and photosensitive resin component shown in Table 4. Formed. Next, the cured pattern and the electrode pattern were evaluated by the above evaluation method. The results are shown in Table 5. The film thickness of the photosensitive paste layer was in the range of 10 μm ± 1 μm.

[Example 17]
Aluminum powder A1 (16 g) shown in Table 1, glass powder B1 (2 g) shown in Table 2, and photosensitive resin component (6) (82 g) shown in Table 3 were kneaded with a kneader to prepare a photosensitive paste composition ( Hereinafter also referred to as “photosensitive paste”).

Two polyethylene terephthalate (PET) films (width: 200 mm, length: 30 m, thickness: 50 μm) that had been subjected to release treatment in advance were prepared as support films.
Next, on one support film, the photosensitive paste is applied by a roll coater to form a coating film, and the formed coating film is dried at 100 ° C. for 5 minutes to remove the solvent. A 10 μm photosensitive paste layer was formed.

Next, the other support film was bonded to the photosensitive paste layer, and thermocompression bonded with a heating roller. The pressure bonding conditions were such that the surface temperature of the heating roller was 90 ° C., the roll pressure was 4 kg / cm ² , and the moving speed of the heating roller was 0.5 m / min. In this manner, a transfer film having a photosensitive paste layer (thickness 10 μm) was produced.

Next, one support film is peeled off, the photosensitive paste layer is overlaid on the surface of a glass substrate which is a test piece (150 × 150 × 2.8 mm), and the remaining support film is peeled off. The paste layer was thermocompression bonded with a heating roller. Crimping conditions, 90 ° C. The surface temperature of the heating roller, a roll pressure of 4 kg / cm ^2, the moving speed of the heating roller was set to 0.5 m / min.

  As a result, the photosensitive paste layer was transferred and adhered to the surface of the glass substrate. When the thickness of the transferred photosensitive paste layer was measured, it was in the range of 10 μm ± 1 μm.

Next, using a negative chrome mask (pattern width 50 μm, pattern interval 100 μm), the photosensitive paste 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 500 mJ / cm ² .

  Next, the exposed photosensitive paste layer was developed by applying a 0.5% aqueous solution of sodium carbonate 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 exposure pattern was formed on the glass substrate. The exposure pattern after this development was evaluated by the above evaluation method. The results are shown in Table 4.

  Next, the obtained exposure pattern was baked at 580 ° C. for 30 minutes to form an electrode pattern. The electrode pattern after firing was evaluated by the above evaluation method. The results are shown in Table 4.

[Example 18]
Example except that a photosensitive paste was prepared using aluminum powder A1 (45 g) shown in Table 1, glass powder B1 (5 g) shown in Table 2, and photosensitive resin component (5) (50 g) shown in Table 3. In the same manner as in No. 1, a photosensitive paste layer, a cured pattern, and an electrode pattern were sequentially formed on a glass substrate. Next, the cured pattern and the electrode pattern were evaluated by the above evaluation method. The results are shown in Table 4.

[Example 19]
Example except that a photosensitive paste was prepared using aluminum powder A1 (35 g) shown in Table 1, glass powder B1 (20 g) shown in Table 2, and photosensitive resin component (5) (45 g) shown in Table 3. In the same manner as in No. 1, a photosensitive paste layer, a cured pattern, and an electrode pattern were sequentially formed on a glass substrate. Next, the cured pattern and the electrode pattern were evaluated by the above evaluation method. The results are shown in Table 4.

[Example 20]
Example except that a photosensitive paste was prepared using aluminum powder A1 (20 g) shown in Table 1, glass powder B1 (30 g) shown in Table 2, and photosensitive resin component (5) (50 g) shown in Table 3. In the same manner as in No. 1, a photosensitive paste layer, a cured pattern, and an electrode pattern were sequentially formed on a glass substrate. Next, the cured pattern and the electrode pattern were evaluated by the above evaluation method. The results are shown in Table 4.

ＴＭＰ：トリメチロールプロパン（プロピオンオキサイド変性）トリアクリレート
ＭＴＰＭＰ：２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノ−１−プロパン−１−オン
ＤＥＴＸ：２，４−ジエチルチオキサントン
ＢＨＨＤ：１，７−ビス（４−ヒドロキシフェノール）−１，６−ヘプタジエン−３，５−ジオン
ＴＮＯＬ：ターピネオール
ＰＧＭＥ：プロピレングリコールモノメチルエーテル

TMP: trimethylolpropane (propion oxide modified) triacrylate MTPMP: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propan-1-one DETX: 2,4-diethylthioxanthone BHHD: 1,7-bis (4-hydroxyphenol) -1,6-heptadiene-3,5-dione TNOL: terpineol PGME: propylene glycol monomethyl ether

表４に示すように、現像後および焼成後のパターン評価では、実施例１〜６、１０〜１２、１７〜２０が特に優れていた。実施例７〜９、１３、１４および１６は良好であった。実施例１５はやや良好であった。また、体積抵抗の評価では、実施例１〜１５、１７〜２０は５０〜２００μΩ・ｃｍの範囲に入った。実施例１６は４００〜６００μΩ・ｃｍの範囲に入った。

As shown in Table 4, Examples 1 to 6, 10 to 12, and 17 to 20 were particularly excellent in pattern evaluation after development and after baking. Examples 7-9, 13, 14 and 16 were good. Example 15 was slightly better. Moreover, in evaluation of volume resistance, Examples 1-15 and 17-20 entered the range of 50-200 microhm * cm. Example 16 entered the range of 400 to 600 μΩ · cm.

[Comparative Example 1]
A photosensitive paste layer, a cured pattern, and an electrode pattern were sequentially formed on a glass substrate in the same manner as in Example 1 except that a photosensitive paste was prepared using the aluminum powder, glass powder, and photosensitive resin component shown in Table 5. Formed. Next, the cured pattern and the electrode pattern were evaluated by the above evaluation method. The results are shown in Table 5.

表５に示すように、現像後および焼成後のパターン評価では、比較例１は凝集またはゲル化が発現し、評価できなかった。また、電極パターンの剥れが観察された。体積抵抗の評価では、比較例１は４００〜６００μΩ・ｃｍの範囲に入った。

As shown in Table 5, in the pattern evaluation after development and after baking, Comparative Example 1 exhibited aggregation or gelation and could not be evaluated. Moreover, peeling of the electrode pattern was observed. In the evaluation of volume resistance, Comparative Example 1 was in the range of 400 to 600 μΩ · cm.

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

Claims (7)

An aluminum powder (A) having a 50% by weight particle diameter (D50) of 2.0 to 20.0 μm and a fatty acid clathrate,
Alkali-soluble resin (C),
A photosensitive paste composition comprising a polyfunctional (meth) acrylate (D) and a photopolymerization initiator (E).   2. The photosensitive paste composition according to claim 1, wherein the content of the aluminum powder (A) is 15 to 70 wt% with respect to the entire photosensitive paste composition.   The alkali-soluble resin (C) is derived from at least one alkali-soluble functional group-containing monomer (C1) selected from carboxyl group-containing monomers, hydroxyl group-containing monomers, and phenolic hydroxyl group-containing monomers in all the structural units. The photosensitive paste composition according to claim 1, which is a resin containing 5 to 90% by weight of the structural unit.   The photosensitive paste composition according to any one of claims 1 to 3, wherein the acid value of the alkali-soluble resin (C) is 20 to 200 mgKOH / g.   The photosensitive paste composition according to any one of claims 1 to 4, further comprising a glass powder (B) having a 50 wt% particle size (D50) of 0.2 to 4.0 µm. .   6. The glass powder (B) containing a glass powder having a softening point of 350 to 700 ° C. in a proportion of 0.5 to 15% by weight with respect to the entire photosensitive paste composition. The photosensitive paste composition described in 1. Forming a photosensitive paste layer comprising the photosensitive paste composition according to any one of claims 1 to 6 on a substrate;
A step of exposing the paste layer to form a latent image of a pattern;
A pattern forming method comprising: a step of developing the paste layer to form a pattern; and a step of baking the pattern in this order.

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