JP5120119B2 - Photosensitive paste composition and pattern forming method - Google Patents

Description

  The present invention relates to a photosensitive paste composition and a pattern forming method. More specifically, in the manufacture of circuit boards having fine patterns such as electrodes used in display panels such as flat panel displays, advanced mounting materials for electronic components and solar cell materials, high-sensitivity and high-precision patterns are formed. The present invention relates to a photosensitive paste composition and a pattern forming method that can be suitably used in some cases.

  In recent years, there is an increasing demand for higher density and higher definition for pattern formation on circuit boards and display panels. Among such display panels that are in increasing demand, 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”). (Also called).

  FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC type PDP. In FIG. 1, reference numerals 101 and 102 denote opposing glass substrates, and reference numerals 103 and 111 denote partition walls. Cells are partitioned by the glass substrate 101, the glass substrate 102, the rear partition wall 103, and the front partition wall 111. 104 is a transparent electrode fixed to the glass substrate 101, 105 is a bus electrode formed on the transparent electrode 104 for the purpose of reducing the resistance of the transparent electrode 104, and 106 is an address electrode fixed to the glass substrate 102. It is. 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, 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 the FPD represented by the PDP having the above-described configuration, the panel has been increased in size and definition, and accordingly, improvement of the pattern forming 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.

  By using the photosensitive silver paste, for example, in the manufacture of electrodes by the above photolithography method, large-sized and high-definition patterns that are problems that cannot be dealt with by the screen printing method can be formed.

  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 the silver surface easily causes sulfidation.

Therefore, due to the recent demand for cost, an inorganic particle-containing photosensitive resin material capable of forming an inexpensive and high-definition pattern is desired.
JP 2002-313231 A

  Examples of inorganic particles that can replace expensive silver include aluminum. However, since aluminum is more easily oxidized than silver, there is a problem in that the resistance value increases in the firing process.

  An object of the present invention is to provide a photosensitive paste composition that can solve the problems associated with the prior art as described above and can form a low-definition and high-definition pattern at low cost. And Another object of the present invention is to provide a pattern forming method using the photosensitive paste composition.

  The present inventors have intensively studied to solve the above problems. As a result, it has been found that by using a specific organometallic compound together with the aluminum powder, the aluminum powder can be prevented from being oxidized, and the present invention has been completed. That is, the present invention relates to the following [1] to [7].

  [1] At least one metal powder (A) selected from aluminum powder and aluminum alloy powder, alkali-soluble resin (C), polyfunctional (meth) acrylate (D), photopolymerization initiator (E), solvent ( F) and an organometallic compound (G) containing a metal selected from Al, Li and Mg.

  [2] The photosensitive paste composition according to [1], wherein the organometallic compound (G) is at least one organometallic compound selected from a carboxylic acid metal salt and an acetylacetone metal complex. .

[3] The photosensitive paste composition as described in [1] or [2] above, wherein the metal powder (A) has an average particle size (D50) of 1.0 to 10.0 μm.
[4] The glass powder (B) is further included, the glass powder (B) has an average particle size (D50) of 0.2 to 4.0 μm, and a maximum particle size (D _max ) of 30 μm or less. The photosensitive paste composition according to any one of [1] to [3], which is characterized in that

  [5] The glass powder (B) includes a glass powder having a softening point of 300 to 700 ° C. in a proportion of 0.5 to 35% by weight with respect to the entire photosensitive paste composition. The photosensitive paste composition as described in [4] above.

  [6] The photosensitivity according to any one of [1] to [5], wherein the metal powder (A) is contained in a proportion of 10 to 70% by weight with respect to the entire photosensitive paste composition. Paste composition.

  [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 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.

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

  Moreover, by using the photosensitive paste composition of the present invention, it is possible to form a pattern having excellent advantages and a low resistance while having the above advantages.

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

[Photosensitive paste composition]
The photosensitive paste composition of the present invention contains a metal powder (A), a photosensitive resin component, and an organometallic compound (G) described below as essential components. The said photosensitive resin component is comprised from the photosensitive resin which consists of alkali-soluble resin (C), polyfunctional (meth) acrylate (D), and a photoinitiator (E), and a solvent (F).
Moreover, you may mix | blend glass powder (B), another additive, etc. as an arbitrary component other than the said component with the photosensitive paste composition of this invention.

<Metal powder (A)>
The metal powder (A) used in the present invention is at least one metal powder selected from aluminum powder and aluminum alloy powder. The shape of the metal powder (A) is not particularly limited, and spherical or flaky powder can be used.

  The average particle diameter of the metal powder (A) is preferably 50% by weight average particle diameter (D50) in the range of 1.0 to 10.0 μm, more preferably 2.0 to 8.0 μm. When the average particle diameter (D50) of the metal powder (A) is in the above range, light at the time of ultraviolet irradiation can sufficiently reach the bottom of the photosensitive paste 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 method.

  The content of the metal powder (A) is preferably in the range of 10 to 70% by weight, more preferably 15 to 50% by weight, based on the entire photosensitive paste composition. When content of metal powder (A) exists in the said range, the pattern which is excellent in electroconductivity can be formed.

Further, in the photosensitive paste composition of the present invention, other metal powders (for example, Pt, Au, Ag, Cu, Sn, Ni, Fe, Zn, W, 100 parts by weight of the metal powder (A)). Mo and their compounds) may be blended within 25 parts by weight.
By mix | blending the above-mentioned metal powder (A), an inexpensive and high-definition pattern can be formed using the photosensitive paste composition of this invention.

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

  For example, when forming the electrode which comprises FPD, the softening point becomes like this. Preferably it is 300-700 degreeC, More preferably, the glass powder which exists in the range of 400-620 degreeC is used. When the softening point of the glass powder is lower than the above range, the glass powder may melt at the stage where the organic substance such as the binder resin is not completely decomposed and removed in the baking process of the photosensitive paste layer. For this reason, a part of the organic substance remains in the formed electrode, and as a result, the electrode tends to be colored and its light transmittance tends to decrease. On the other hand, when the softening point of the glass powder exceeds the above range, it is necessary to fire at a temperature higher than the softening point, so that the glass substrate is likely to be distorted.

The glass powder having a softening point in the above range is preferably contained in an amount of 0.5 to 35% by weight, more preferably 5.0 to 30.0% by weight, based on the entire photosensitive paste composition. When content of the said glass powder exists in the said range, the pattern which is excellent in adhesiveness with a support body can be formed.

As a preferable specific example of the 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. Lead oxide, boron oxide, silicon oxide, aluminum oxide (PbO—B ₂ O ₃ —SiO ₂ —
A mixture of 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. Zinc oxide, phosphorus oxide, silicon oxide, aluminum oxide (ZnO—P ₂ O ₅ —SiO ₂ —
A mixture of Al ₂ O ₃ system),
10. A mixture of zinc oxide, phosphorus oxide, titanium oxide (ZnO—P ₂ O ₅ —TiO ₂ system),
11. Zinc oxide, boron oxide, silicon oxide, potassium oxide (ZnO—B ₂ O ₃ —SiO ₂ —
K ₂ O-based) mixture,
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). Of these, lead-free glass powders that are environmentally friendly are particularly preferred.

  The average particle size of the glass powder (B) is appropriately selected in consideration of the shape of the pattern to be formed, but the 50% by weight average particle size (D50) of the glass powder (B) is preferably 0.2 to It is 4.0 μm, more preferably in the range of 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 powder (B) is in the above range, light at the time of ultraviolet irradiation sufficiently reaches the bottom of the photosensitive paste layer, and a high-definition pattern can be obtained.

Moreover, the maximum particle diameter ( _Dmax ) of glass powder (B) becomes like this. Preferably it is 30 micrometers or less, More preferably, it exists in the range of 10-20 micrometers. When the maximum particle diameter of the glass powder (B) is in the above range, a pattern having excellent resolution can be formed.

  The content of the glass powder (B) is preferably 8 to 50% by weight, more preferably 10 to 40% by weight, and still more preferably with respect to the total 100% by weight of the metal powder (A) and the glass powder (B). It is in the range of 12 to 35% by weight. When the content of the glass powder (B) is in the above range, the metal powder (A) can be prevented from being oxidized in the firing step, and a low-resistance electrode can be produced. Moreover, the said electrode is excellent also in adhesiveness with a board | substrate.

The total content of the metal powder (A) and the glass powder (B) is the metal powder (A), the glass powder (B), the alkali-soluble resin (C), the polyfunctional (meth) acrylate (D) and the light. Preferably it is 60-80 weight% with respect to a total of 100 weight% of a polymerization initiator (E), More preferably, it is 65-80 weight%, More preferably, it exists in the range of 70-75 weight%. When the total content of the metal powder (A) and the glass powder (B) is in the above range, oxidation of the metal powder (A) can be prevented in the firing step, and a low resistance electrode can be produced. Moreover, the said electrode is excellent also in adhesiveness with a board | substrate.

<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” refers to 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 acid mono (2- (meth)). Acryloyloxyethyl), 2-methacryloyloxyethylphthalic acid, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2-acryloyloxypropyl tetrahydrophthalate, carboxyl group-containing monomers such as ω-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 thereof 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, (meth) acrylic acid, 2-methacryloyloxyethylphthalic acid, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2-acryloyloxy Propyltetrahydrophthalate 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 structural unit derived from the alkali-soluble functional group-containing monomer (C1) is usually from 5 to 90% by weight, preferably from 10 to 80% by weight, particularly preferably in all the structural units of the alkali-soluble resin (C). It is in the range of 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) Alkali-soluble, such as acrylate, phenoxyethyl (meth) acrylate, trityl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate, etc. Functional group-containing monomer (C1) other than (meth) acrylates and the like.

  In the present invention, for example, styrene, methyl (meth) acrylate, ethyl (meth) acrylate instead of the (meth) acrylic acid derivative (C2) or in addition to the (meth) acrylic acid derivative (C2). 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 benzyl (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-butyl Examples thereof include organic peroxides of peroxyesters such as peroxy 2-ethylhexanoate and cumyl peroxy 2-ethylhexanoate. These radical polymerization initiators may be used alone or in combination of two or more.
The amount of the radical polymerization initiator used is usually about 0.1 to 10 parts by weight with respect to 100 parts by weight of all monomers (including macromonomer, the same applies hereinafter) used for the copolymerization.

≪Chain transfer agent≫
In the copolymerization, a chain transfer agent may be used. Examples of the chain transfer agent include α-methylene styrene dimer, t-dodecyl mercaptan, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), trimethylolpropane tris (3-mercapto). Propionate), tetraethylene glycol bis (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane, and the like.

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 (hereinafter also referred to as “GPC”), preferably 5000 to 100,000. Preferably it is 10000-80000. Mw can be controlled by appropriately selecting conditions such as the copolymerization ratio, composition, chain transfer agent, polymerization temperature and the like of the monomers (C1) and (C2). When Mw is lower than the above range, film roughness after development tends to occur. On the other hand, if Mw exceeds the above range, the solubility of the unexposed area in the developer may be lowered, and the resolution may be lowered.

  The alkali-soluble resin (C) has a glass transition temperature (Tg) of usually 0 to 120 ° C, preferably 10 to 100 ° C. When the glass transition temperature is lower than the above range, the coating film tends to be tacky and handling tends to be difficult. 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 a transfer film described later is used, transfer may not be performed satisfactorily. In addition, the said glass transition temperature can be suitably adjusted by changing the quantity of the said alkali-soluble functional group containing monomer (C1) and (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 lower than the above range, 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 the above range, 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.

  The content of the alkali-soluble resin (C) is preferably 20 to 80% by weight, more preferably 50 to 70% by weight with respect to the photosensitive resin. When the content of the alkali-soluble resin (C) is in the above range, the dispersibility of the metal powder (A) and the glass powder (B) in the photosensitive paste composition and the pattern developability are excellent.

<Multifunctional (meth) acrylate (D)>
Examples of the polyfunctional (meth) acrylate (D) used in the present invention include 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, triglycerol (Meth) di (meth) methacrylate such as acrylate;
Pentaerythritol tri (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylolpropane (propylene oxide modified) tri (meth) acrylate, trimethylolpropane (ethylene oxide modified) tri (meth) acrylate, dipentaerythritol hexa (meta) ) Acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, trifunctional or more (meth) acrylates such as benzyl mercaptan (meth) acrylate;
Mention may be made, for example, of monomers in which 1 to 5 of the hydrogen atoms of the aromatic ring in the compound are substituted with chlorine or bromine atoms. Polyfunctional (meth) acrylate (D) may be used individually by 1 type, or may use 2 or more types together.

  The content of the polyfunctional (meth) acrylate (D) is usually 10% by weight or more, preferably 15 to 60% by weight with respect to the photosensitive resin from the viewpoint of sensitivity to exposure light. When content of polyfunctional (meth) acrylate (D) exceeds the said range, the shape of the member for display panels after baking may deteriorate, for example.

  Further, styrene, p-methyl styrene, o-methyl styrene, m-methyl styrene, chlorinated styrene, brominated styrene, α-methyl styrene, chlorinated α-methyl styrene, bromine within the range not impairing the object of the present invention. Α-methylstyrene, chloromethylstyrene, hydroxymethylstyrene, carboxymethylstyrene, vinylnaphthalene, vinylanthracene, vinylcarbazole, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone, etc. Good.

<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 photoreducing dye such as eosin or methylene blue and a reducing agent such as ascorbic acid or triethanolamine. These may be used alone or in combination of two or more.

  A sensitizer may be used together with the photopolymerization initiator in order to improve the exposure sensitivity of the photosensitive paste 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, Michler's ketone, 4,4- Bis (diethylamino) -benzophenone, 4,4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 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 sensitizers may be used alone or in combination of two or more. Some sensitizers also act as photopolymerization initiators.

  The content of the photopolymerization initiator (E) (when the sensitizer is also used, the content of the photopolymerization initiator and the sensitizer) is usually based on 100 parts by weight of the polyfunctional (meth) acrylate (D). Is in the range of 1-50 parts by weight, preferably 2-40 parts by weight. When content of a photoinitiator (E) exceeds the said range, the shape of the member for display panels after baking may deteriorate, for example.

<Solvent (F)>
The solvent (F) used by this invention is used in order to adjust the viscosity of the photosensitive paste composition. Examples of the solvent (F) include terpineol, dihydroterpineol, dihydroterpinel acetate, limonene, carveol, 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, dibromoben Emissions, dichlorobenzene, bromobenzoic acid, and organic solvents such as chlorobenzoic acid. A solvent (F) may be used individually by 1 type, or may use 2 or more types together.
Content of a solvent (F) is 30 to 80 weight% normally with respect to 100 weight% of photosensitive resin components, Preferably it exists in the range of 40 to 70 weight%.

<Organic metal compound (G)>
The organometallic compound (G) used in the present invention is an organometallic compound containing a metal selected from Al, Li and Mg. In this invention, the resistance value of a sintered compact can be reduced by mix | blending an organometallic compound (G).

  Examples of the organometallic compound containing the metal include carboxylic acid metal salts such as naphthenic acid and octylic acid, and acetylacetone metal complexes. The said organometallic compound may be used individually by 1 type, and may use 2 or more types together.

  Specific examples of the organometallic compound (G) include aluminum naphthenate, aluminum octylate, aluminum acetylacetonate; lithium naphthenate, lithium octylate, lithium acetylacetonate; magnesium naphthenate, magnesium octylate, magnesium acetylacetonate Etc.

  The content of the organometallic compound (G) is preferably 2% by weight or more, more preferably 3 to 20% by weight with respect to the entire photosensitive paste composition from the viewpoint of development characteristics. If the content of the organometallic compound (G) is within the above range, it is considered that the metal powder (A) can be prevented from being oxidized in the firing step, and the resistance value of the sintered body can be reduced. When the content of the organometallic compound (G) is below the above range, the effect of adding the compound (G) is not observed, and when the content exceeds 20% by weight, the development characteristics may be poor. is there.

<Other additives>
The photosensitive paste composition of the present invention includes an ultraviolet absorber, a polymerization inhibitor, an antioxidant, an adhesion assistant, a dissolution accelerator, a sensitizer, a plasticizer, a thickener, a dispersant, and precipitation of the above components. You may mix | blend additives, such as an inhibitor and a leveling agent.

≪Ultraviolet absorber≫
An ultraviolet absorber may be added to the photosensitive paste composition of the present invention. 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, organic dyes and inorganic pigments can be used. Among them, organic dyes and inorganic pigments having a high ultraviolet absorption coefficient in a wavelength range of 350 to 450 nm are 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 dyes such as:
Examples include 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.

  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 the added amount of the inorganic pigment is less than the above range, the effect of adding the UV absorber is reduced, and if it exceeds the above range, the effect of the UV absorber is so great that light cannot reach the lower part of the photosensitive paste layer and the pattern cannot be formed. In some cases, the film forming strength cannot be maintained.

≪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 composition in an amount preferably in the range of 0.001 to 1% by weight.

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

≪Adhesion aid≫
An adhesion aid may be added to the photosensitive paste composition of the present invention in order to improve the adhesion between the photosensitive paste layer and a support such as a glass substrate. 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 adhesion assistant can be added in an amount of 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).

≪Solution 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 the surfactant include a fluorine-based surfactant, a silicone-based surfactant, a nonionic surfactant, and a fatty acid.

  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. Commercial products.

  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”, “No. 90” manufactured by Kyoeisha Chemical Co., Ltd., and the like.

  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 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 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 1
Is an integer of -5, s is an integer of 1 to 5, preferably 2, and t is an integer of 1 to 100, preferably an integer of 10 to 20.

  The content of the dissolution accelerator is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, particularly preferably 0.1 to 0.1 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (C). It is in the range of 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 is prepared by mixing the above-described components so as to have a predetermined composition ratio, and then uniformly mixing and dispersing them with a three roll or kneader. The viscosity of the composition can be appropriately adjusted depending on the addition amount of inorganic particles such as metal powder (A) and glass powder (B), solvent (F), thickener, plasticizer, and precipitation inhibitor. The range is usually 100 to 500,000 cps (centipoise).

[Pattern formation method]
The pattern forming method of the present invention comprises a step of forming a photosensitive paste layer comprising the photosensitive paste composition on a substrate (photosensitive paste layer forming step), and exposing the paste layer to form a latent image of the pattern. And a step of developing the 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: (i) a method in which the photosensitive paste composition is applied on a substrate to form a coating film, and the coating film is dried; A method of transferring the paste layer onto a substrate using a transfer film having a photosensitive paste layer obtained by applying a conductive paste composition on a support film to form a coating film and drying the coating film, etc. Is mentioned.

(I) As a method for applying the photosensitive paste composition on a substrate, any method can be used as long as it can efficiently form a coating film having a large film thickness (for example, 20 μm or more) and excellent uniformity. It is not limited. Examples include a coating method using a knife coater, a coating method using a roll coater, a coating method using a doctor blade, a coating method using a curtain coater, a coating method using a die coater, 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 film thickness of the photosensitive paste layer formed as described above is usually 3 to 300 μm, 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 said composition n times.

  (Ii) An example of the transfer process using the transfer film having the photosensitive paste layer is shown below. The transfer film is overlaid so that the surface of the photosensitive paste layer is in contact with the surface of the substrate, and the transfer film is thermocompression bonded with a heating roller or the like, and then the support film is peeled off from the paste layer. As a result, the photosensitive paste layer is transferred and adhered to the surface of the substrate.

The support film is preferably a resin film having heat resistance and solvent resistance and flexibility. Examples of the resin that forms the support film include polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, polyfluoroethylene, and other fluorine-containing resins, nylon, and cellulose.

As the transfer conditions, for example, the surface temperature of the heating roller is 10 to 200 ° C., the roll pressure by the heating roller is 0.5 to 10 kg / cm ² , and the moving speed of the heating roller is 0.1 to 10 m / min. Moreover, the said board | substrate may be preheated and the preheating temperature is 40-140 degreeC, for example.

  Examples of the substrate material used in the present invention include a plate-like member made of an insulating material such as glass, silicone, polycarbonate, polyester, aromatic amide, polyamideimide, and polyimide. In these, it is preferable to use the glass substrate which has heat resistance.

<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. Specifically, the surface of the photosensitive paste layer is selectively irradiated with radiation such as ultraviolet rays through an exposure mask to form a pattern latent image on the paste layer.

  As the exposure is performed by ordinary photolithography, a mask exposure method using a photomask can be employed. The exposure pattern of the photomask is a stripe or lattice having a width of 10 to 500 μm, for example, depending on the purpose.

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.
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. When exposing a large area, a photosensitive paste layer is formed on a substrate such as a glass substrate, and then exposing while transporting to expose a large area with an exposure machine having a small exposure area. Can do.

  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, 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 using the difference in solubility in the developer between the photosensitive portion and the non-photosensitive portion to form a pattern of the paste layer. 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 photosensitive resin in the photosensitive paste layer can be used. In addition, 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.

  In the present invention, the photosensitive paste layer contains inorganic particles such as metal powder (A) and glass powder (B), but the inorganic particles are uniformly dispersed by the alkali-soluble resin (C). The inorganic particles are also removed simultaneously 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, more preferably 0.1 to 5% by weight. If the alkali concentration is too low, the soluble portion is not removed, and if the alkali concentration is too high, the pattern portion may be peeled off and the non-soluble portion may be corroded. The development temperature during development is preferably 20 to 50 ° C. in terms of process control.

  The alkaline aqueous solution may contain the above-described nonionic surfactant or organic solvent. In addition, after the development process with an alkali developer, a washing process is usually performed.

<Baking process>
In order to burn off the organic substance contained in the photosensitive paste layer remaining portion (pattern of the paste layer) after the development, the pattern of the paste layer is baked in a baking furnace.

  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 pattern be burned out, and thus 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.

<Heating process>
A heating step of 50 to 300 ° C. may be introduced during the photosensitive paste layer formation, exposure, development, and baking steps for the purpose of drying or preliminary reaction.

[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. The manufacturing method of the FPD member is particularly suitable for manufacturing 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 of measuring weight average molecular weight (Mw) and weight average molecular weight (Mw) / number average molecular weight (Mn) (hereinafter also 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.
(width)
A: The desired standard.
B: Desired standard within ± 3 μm.
C: A desired standard exceeding ± 3 μm and within ± 5 μm.
D: Desired standard exceeds ± 5 μm.
(height)
A: The desired standard.
B: Desired standard within ± 2 μm.
C: A desired standard exceeding ± 2 μm and within ± 4 μm.
D: Over the desired standard ± 4 μm.

[Evaluation of adhesion of pattern 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.

Cellotape (registered trademark) (manufactured by Nichiban Co., Ltd.) was thermocompression bonded to the support surface 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.

Thereby, the cellophane (registered trademark) was transferred to the surface of the support and brought into close contact. By peeling this cello tape (registered trademark) from the support, the adhesion between the pattern and the support was evaluated.
○: No pattern peeling.
X: Pattern peeling occurred.

[Synthesis Example 1]
Methacrylic acid 15 parts, 2-hydroxyethyl methacrylate 15 parts, n-butyl methacrylate 40 parts, 2-ethylhexyl methacrylate 30 parts, azobisisobutyronitrile (AIBN) 1 part, pentaerythritol tetrakis (3-mercaptopropionate) 3 parts (manufactured by Sakai Chemical Industry Co., Ltd.) were charged into an autoclave equipped with a stirrer and stirred in 120 parts of dihydroterpineol 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 C1. The polymerization rate of the alkali-soluble resin C1 was 98%, and the weight-average molecular weight of the alkali-soluble resin C1 was 20000 (Mw / Mn = 2).

[Synthesis Example 2]
In Synthesis Example 1, except that 1 part of trimethylolpropane tris (3-mercaptopropionate) (manufactured by Sakai Chemical Industry Co., Ltd.) was used instead of 3 parts of pentaerythritol tetrakis (3-mercaptopropionate). In the same manner as in Synthesis Example 1, an alkali-soluble resin C2 was obtained. The polymerization rate of the alkali-soluble resin C2 was 98%, and the weight-average molecular weight of the alkali-soluble resin C2 was 22000 (Mw / Mn = 2).

[Synthesis Example 3]
In Synthesis Example 1, except that 1 part of tetraethylene glycol bis (3-mercaptopropionate) (manufactured by Sakai Chemical Industry Co., Ltd.) was used instead of 3 parts of pentaerythritol tetrakis (3-mercaptopropionate). In the same manner as in Synthesis Example 1, an alkali-soluble resin C3 was obtained. The polymerization rate of the alkali-soluble resin C3 was 98%, and the weight-average molecular weight of the alkali-soluble resin C3 was 25000 (Mw / Mn = 2).

[Preparation of photosensitive resin components (1) to (5)]
Photosensitive resin components (1) to (5) having the compositions shown in Table 1 were prepared.

［実施例１］
金属粉末（Ａ）として表２に示すアルミニウム粉末Ａ１（５０ｇ）、ガラス粉末（Ｂ）として表３に示すガラス粉末Ｂ１（５ｇ）、表１に示す感光性樹脂成分（１）（４２ｇ）、および有機金属化合物（Ｇ）としてアルミニウムアセチルアセトネート（３ｇ）を混練機で混練して、感光性ペースト組成物を調製した。

[Example 1]
Aluminum powder A1 (50 g) shown in Table 2 as metal powder (A), Glass powder B1 (5 g) shown in Table 3 as glass powder (B), Photosensitive resin component (1) (42 g) shown in Table 1, and Aluminum acetylacetonate (3 g) as an organometallic compound (G) was kneaded with a kneader to prepare a photosensitive paste composition.

  The photosensitive paste composition is printed on a glass substrate (150 mm × 150 mm × 2.8 mm) using a 325 mesh screen to a size of 100 mm square, dried at 120 ° C. for 20 minutes, and dried. An adhesive paste layer was formed. The film thickness of the photosensitive paste layer was in the range of 10 μm ± 1 μm.

Next, the above-mentioned photosensitive paste layer was exposed to ultraviolet rays from the upper surface using a negative chrome mask (pattern width: 50 μm, pattern interval: 100 μm) with an ultrahigh pressure mercury lamp of 25 mW / cm ² output. The exposure amount was 100 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 said glass substrate. The obtained cured pattern 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 14]
In 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 composition having the composition shown in Table 4 was prepared. Subsequently, these were evaluated by the above evaluation method. The results are shown in Table 4.

[Example 15]
Aluminum powder A1 (42 g) shown in Table 2 as aluminum powder (A), glass powder B1 (3 g) shown in Table 3 as glass powder (B), photosensitive resin (1) (55 g) shown in Table 1, and organic Aluminum acetylacetonate (3 g) as a metal compound (G) was kneaded with a kneader to prepare a photosensitive paste composition.

  As a support film, two pieces of polyethylene terephthalate (PET) film (width 200 mm, length 30 m, thickness 50 μm) which have been subjected to release treatment in advance are prepared, and the photosensitive paste composition is placed on one support film using a roll coater. A coating film was formed by coating, and the formed coating film was dried at 120 ° C. for 60 minutes to remove the solvent, thereby forming a photosensitive paste layer having a thickness of 10 μm.

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. Thus, the transfer film which has a 10-micrometer-thick photosensitive paste layer was produced.

Next, one support film is peeled off, the photosensitive paste layer is overlaid on the surface of a glass substrate (150 × 150 × 2.8 mm), which is a test piece, and the remaining support film is peeled off. The paste layer was 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.
As a result, the photosensitive paste layer was transferred and adhered to the surface of the glass substrate. When the film thickness of the transferred photosensitive paste layer was measured, the film thickness was in the range of 10 μm ± 1 μm.

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

表４に示すように、実施例１〜１５におけるパターン評価では、実施例１、４〜９、１３〜１５が特に優れていた。実施例２および１１は良好であった。実施例３、１０および１２はやや良好であった。また、実施例１〜１５において、電極パターンの欠けや剥れなどは見られなかった。実施例１〜１５における体積抵抗の評価では、２５〜７０μΩ・ｃｍの範囲に入る結果となった。

As shown in Table 4, in the pattern evaluation in Examples 1 to 15, Examples 1, 4 to 9, and 13 to 15 were particularly excellent. Examples 2 and 11 were good. Examples 3, 10 and 12 were slightly better. In Examples 1 to 15, no chipping or peeling of the electrode pattern was observed. The evaluation of the volume resistance in Examples 1 to 15 resulted in a range of 25 to 70 μΩ · cm.

[Comparative Examples 1-4]
In 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 composition having the composition shown in Table 5 was prepared. Subsequently, these were evaluated by the above evaluation method. The results are shown in Table 5.

[Comparative Example 5]
In Example 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 15 except that a photosensitive paste composition having the composition shown in Table 5 was prepared. Subsequently, these were evaluated by the above evaluation method. The results are shown in Table 5.

表５に示すように、比較例１〜５におけるパターン評価では、何れも不良であり、電極パターンの欠けが観察された。また、比較例３〜５においては、電極パターンと支持体との密着性不良が観察された。比較例１〜５における体積抵抗の評価では、２００〜３００μΩ・ｃｍの範囲に入る結果となった。

As shown in Table 5, in the pattern evaluation in Comparative Examples 1-5, all were bad, and the lack of the electrode pattern was observed. In Comparative Examples 3 to 5, poor adhesion between the electrode pattern and the support was observed. The evaluation of volume resistance in Comparative Examples 1 to 5 resulted in a range of 200 to 300 μΩ · cm.

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.

Explanation of symbols

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 (7)

At least one metal powder (A) selected from aluminum powder and aluminum alloy powder,
Alkali-soluble resin (C),
Polyfunctional (meth) acrylate (D),
Photopolymerization initiator (E),
Solvent (F) and organometallic compound (G) containing a metal selected from Al, Li and Mg
A photosensitive paste composition comprising:   The photosensitive paste composition according to claim 1, wherein the organometallic compound (G) is at least one organometallic compound selected from a carboxylic acid metal salt and an acetylacetone metal complex.   The photosensitive paste composition according to claim 1 or 2, wherein an average particle diameter (D50) of the metal powder (A) is 1.0 to 10.0 µm. The glass powder (B) is further contained, the glass powder (B) has an average particle size (D50) of 0.2 to 4.0 μm, and a maximum particle size (D _max ) of 30 μm or less. The photosensitive paste composition in any one of Claims 1-3.   The glass powder having a softening point of 300 to 700 ° C as the glass powder (B) is contained in a proportion of 0.5 to 35% by weight with respect to the entire photosensitive paste composition. The photosensitive paste composition described in 1.   The photosensitive paste composition according to any one of claims 1 to 5, wherein the metal powder (A) is contained in a proportion of 10 to 70% by weight with respect to the entire photosensitive paste composition. 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.

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