JP5120120B2 - 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. In the photolithographic method, for example, in the manufacture of electrodes, by using a photosensitive silver paste, large-size and high-definition patterns, which 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. Furthermore, due to the recent demand for cost, an inorganic particle-containing photosensitive resin material capable of forming an inexpensive and high-definition pattern is required.
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. Furthermore, there is a problem that the adhesion of the pattern obtained after firing to the substrate is poor. For this reason, it was difficult to form a pattern having excellent adhesion to the substrate and low resistance using aluminum.

  The present invention is intended to solve the problems associated with the prior art as described above, is inexpensive and high-definition, is a thin film with high adhesion strength to ceramic, silicon and glass substrates, and has low resistance. It aims at providing the photosensitive paste composition which can form a pattern. Moreover, an object of this invention is to provide the pattern formation method using the said photosensitive paste composition.

  The present inventors have intensively studied to solve the above problems. As a result, by using an aluminum powder having a specific average particle diameter, average circularity, and average length (average ratio of the major axis to the minor axis (major axis / minor axis) of the powder particles), low cost and high definition are achieved. It was found that a conductive pattern having excellent adhesion to the substrate and low resistance can be obtained.

  In addition, by using glass powder in a specific blending amount together with the above aluminum powder, it is found that the aluminum powder can be prevented from being oxidized, and a conductive pattern having a lower resistance can be obtained, and the present invention is completed. It came.

That is, the present invention relates to the following [1] to [3].
[1] An aluminum powder (A), a glass powder (B), an alkali-soluble resin (C), a polyfunctional (meth) acrylate (D), and a photopolymerization initiator (E). 50% by weight particle diameter (D50) is 0.5 to 20.0 μm, the average circularity is 0.7 or more, and the average value of the ratio of the major axis to the minor axis (major axis / minor axis) of the powder particles is 5 or less. And the content of the glass powder (B) is 10 to 30% by weight based on 100% by weight of the total of the aluminum powder (A) and the glass powder (B). .

  [2] The aluminum powder with respect to a total of 100% by weight of the aluminum powder (A), glass powder (B), alkali-soluble resin (C), polyfunctional (meth) acrylate (D) and photopolymerization initiator (E) The total of content of (A) and glass powder (B) is 60 to 80 weight%, The photosensitive paste composition as described in said [1] characterized by the above-mentioned.

  [3] A step of forming a photosensitive resin layer comprising the photosensitive paste composition according to [1] or [2] on a substrate, a step of exposing the resin layer to form a latent image of a pattern, A pattern forming method comprising: a step of developing the resin layer to form a pattern; and a step of baking the pattern.

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

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.
This is presumed to be due to an increase in the number of contacts between aluminum powders by lowering the porosity of the sintered body (that is, improving the filling rate of the sintered body).

  Hereinafter, the photosensitive paste composition and the pattern forming method according to the present invention will be described in detail. In the following description, a layer obtained by using the photosensitive paste composition before exposure is referred to as a “photosensitive resin layer”, and a pattern obtained by exposing and developing the photosensitive resin layer is referred to as a “cured pattern”. The pattern obtained by firing the cured pattern is also referred to as “sintered body”.

[Photosensitive paste composition]
The photosensitive paste composition of the present invention contains inorganic particles and a photosensitive resin. In the present invention, the “inorganic particles” are composed of an aluminum powder (A), a glass powder (B), and another metal powder which is an optional component. The “photosensitive resin” includes an alkali-soluble resin (C), a polyfunctional (meth) acrylate (D), and a photopolymerization initiator (E).
Moreover, you may mix | blend an organic solvent other additive as an arbitrary component with the photosensitive paste composition of this invention other than the said inorganic particle and photosensitive resin.

<Aluminum powder (A)>
As aluminum powder (A) used by this invention, metal powder, such as an aluminum metal and an aluminum alloy, is mentioned, Furthermore, the following requirements are satisfy | filled.

  The aluminum powder (A) has a 50% by weight particle diameter (D50), an average circularity, and an average length in a specific range. In the present invention, the average particle diameter such as 50% by weight particle diameter is a value measured by a laser diffraction method, and the average circularity is (a circle of a circle having the same area as the particle area in the particle projection diagram). Perimeter) / (average length of the contour of the particle in the particle projection diagram), and the average length is the ratio of the major axis to the minor axis of the particle in the particle projection diagram (major axis / short axis). The average value of (diameter).

  The 50 wt% particle size (D50) of the aluminum powder (A) is in the range of 0.5 to 20.0 µm, preferably 1.0 to 15.0 µm, more preferably 2.0 to 10.0 µm. 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.

  The average circularity of the aluminum powder (A) is 0.7 or more, preferably 0.8 or more, more preferably 0.9 or more. If the average circularity of the aluminum powder (A) is less than the above value, there are many voids in the sintered body, and sufficient electrical characteristics cannot be maintained, and the surface of the sintered body becomes rough. There are things to do.

  The average length of the aluminum powder (A) is 5 or less, preferably 3 or less, more preferably 2 or less. When the average length of the aluminum powder (A) exceeds the above value, the light transmittance at the time of ultraviolet irradiation decreases, the coating film cannot be sufficiently cured, and a high-definition pattern may not be obtained. .

  By using the aluminum powder (A) satisfying the above requirements, a pattern having low resistance and excellent adhesion to the substrate can be formed. This is presumed to be due to an increase in the number of contacts between the aluminum powders by lowering the porosity of the sintered body (improving the filling rate of the fired body).

  The photosensitive paste composition of the present invention contains other metal powders (for example, Pt, Au, Ag, Cu, Sn, Ni, Fe, Zn, W, 100 parts by weight of aluminum powder (A)). Mo and their compounds) may be blended within 25 parts by weight.

<Glass powder (B)>
The glass powder (B) used by this invention can be suitably selected according to the use (type of FPD member, electronic component) of the sintered compact formed with the photosensitive paste composition.

  For example, when forming an electrode constituting an FPD, a glass powder having a softening point of preferably 350 to 700 ° C, more preferably 400 to 620 ° C is used. When the softening point of the glass powder is below 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 step of the photosensitive resin 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.

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 particle size (D50) is preferably 0.2 to 4.0 μm, more preferably It exists in the range of 0.5-3.8 micrometers. Moreover, it is preferable that 10 weight% particle diameter (D10) is 0.05-0.5 micrometer, and 90 weight% 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 can sufficiently reach the bottom of the coating film, and a high-definition pattern can be obtained.

In the photosensitive paste composition of the present invention, the content of the glass powder (B) is 10 to 30% by weight, preferably 10 to 10% by weight with respect to the total 100% by weight of the aluminum powder (A) and the glass powder (B). 25% by weight, more preferably 10 to 20% by weight. When the content of the glass powder (B) is in the above range, oxidation of the aluminum 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.

  The total content of aluminum powder (A) and glass powder (B) is aluminum powder (A), glass powder (B), alkali-soluble resin (C), polyfunctional (meth) acrylate (D) and 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 is 70-75 weight%. When the total content of the aluminum powder (A) and the glass powder (B) is within the above range, oxidation of the aluminum powder (A) can be prevented in the firing step, and a low-resistance and high-definition electrode can be manufactured. . 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- (meta ) 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 5 to 90% by weight, preferably 10 to 80% by weight, particularly preferably 15% in all the structural units of the alkali-soluble resin (C). ~ 70 wt%.

≪ (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, Alkali-soluble functional group-containing compounds such as phenoxyethyl (meth) acrylate, trityl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate, etc. Mer (C1) other than (meth) acrylates and the like.

  In the present invention, instead of the (meth) acrylic acid derivative (C2) or together with the (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-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-mercaptopropionic acid), pentaerythritol tetrakis (3-mercaptobutyrate), 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 (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. Moreover, when Mw exceeds the said range, the solubility of the photosensitive resin layer of the unexposed part with respect to a developing solution will fall, and resolution may fall.

  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 handling tends to be difficult. Moreover, when the glass transition temperature exceeds the above range, the adhesion between the photosensitive resin 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 an alkali-soluble functional group containing monomer (C1) and a (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, the photosensitive resin layer in the unexposed area is not easily removed 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.

  In the photosensitive paste composition of the present invention, 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 100% by weight of the photosensitive resin. When the content of the alkali-soluble resin (C) is in the above range, the dispersibility of the inorganic particles and the developability of the pattern in the photosensitive paste composition 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.

  In the photosensitive paste composition of the present invention, the content of the polyfunctional (meth) acrylate (D) is preferably based on 100% by weight of the photosensitive resin from the viewpoint of sensitivity to exposure light used at the time of exposure. Is in the range of 10 wt% or more, more preferably 15-60 wt%. 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.

  As long as the object of the present invention is not impaired, the polyfunctional (meth) acrylate (D), styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, chlorinated styrene, brominated styrene, α- 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 photoreducing dye such as eosin or methylene blue and a reducing agent such as ascorbic acid or triethanolamine. The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.

  In addition to the photopolymerization initiator, a sensitizer may be used to improve the exposure sensitivity of the photosensitive resin layer. Examples of the sensitizer include 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 2,4-diethylthioxanthone, 2,3-bis ( 4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-dimethylaminibenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, 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, An example is 1-phenyl-5-ethoxycarbonylthiotetrazole. The said sensitizer may be used individually by 1 type, and may use 2 or more types together. Some sensitizers also act as photopolymerization initiators.

In the photosensitive paste composition of the present invention, the content of the photopolymerization initiator (E) (the total of the photopolymerization initiator and the sensitizer when a sensitizer is also used) is a polyfunctional (meth) acrylate ( D) Preferably it is 1-50 weight part with respect to 100 weight part, More preferably, it is 2-40 weight part. When content of a photoinitiator (E) exceeds the said range, the shape of the member for display panels after baking may deteriorate, for example.

<Additives>
The photosensitive paste composition of the present invention includes an organic solvent, an ultraviolet absorber, a polymerization inhibitor, an antioxidant, an adhesion assistant, a dissolution accelerator, a sensitizer, a plasticizer, a thickener, a dispersant, an inorganic agent. Particles and photosensitive resin sedimentation inhibitors, leveling agents, and other additives may be added.

≪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 composition. 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. An organic solvent may be used individually by 1 type, and may use 2 or more types together.

≪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: inorganic pigments such as zinc oxide, titanium oxide, and cerium oxide.

  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 ultraviolet absorber is reduced. If the added amount exceeds the above range, the effect of the ultraviolet absorber is so great that light does not reach the lower part of the film and the pattern cannot be formed or the film is formed. Strength may not 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 resin 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 commercially available fluorosurfactants include “BM-1000” and “BM-1100” manufactured by BM CHIMIE, “Megafac F142D” and “Same F172” manufactured by Dainippon Ink & Chemicals, Inc. "F173", "F183", "Florard FC-135", "FC-170C", "FC-430", "FC-431" manufactured by Sumitomo 3M Limited, Asahi Glass Co., Ltd. “Surflon S-112”, “S-113”, “S-131”, “S-141”, “S-145”, “S-382”, “SC-101” , “Same SC-102”, “same SC-103”, “same SC-104”, “same SC-105”, “same SC-106”.

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

Examples of the nonionic surfactant include polyoxyethylene lauryl ether,
Polyoxyethylene alkyl ethers such as polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene distyrenated phenyl ether, polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether And 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 in particular, the following formula (1) ) 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.

  In the photosensitive paste composition of the present invention, the content of the dissolution accelerator is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts per 100 parts by weight of the alkali-soluble resin (C). Part by weight, particularly preferably 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, as essential components, aluminum powder (A), glass powder (B), alkali-soluble resin (C), polyfunctional (meth) acrylate (D) and photopolymerization initiator (E), The above-mentioned various components such as an organic solvent are prepared as optional components so as to have a predetermined composition ratio, and then mixed and dispersed homogeneously with a three roll or kneader.

  The viscosity of the composition can be adjusted as appropriate depending on the amount of inorganic particles, thickener, organic solvent, plasticizer, precipitation inhibitor, etc., but is usually in the range of 100 to 500,000 cps (centipoise). .

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

<Photosensitive resin layer forming step>
In this step, a photosensitive resin layer made of the photosensitive paste composition is formed on the substrate. Examples of the method for forming the photosensitive resin layer include: (i) a method in which the photosensitive paste composition is applied onto a substrate to form a coating film, and the coating film is dried; A method of transferring a resin layer onto a substrate using a transfer film having a photosensitive resin 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 thickness of the photosensitive resin 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 resin 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 resin 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, the transfer film is thermocompression bonded with a heating roller or the like, and then the support film is peeled off from the resin layer. As a result, the photosensitive resin 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 forming the photosensitive resin layer on the substrate by the photosensitive resin layer forming step, exposure is performed using an exposure apparatus. Specifically, the surface of the photosensitive resin layer is selectively irradiated with exposure light such as ultraviolet rays through an exposure mask to form a pattern latent image on the resin 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 method of directly drawing with a red or blue visible light laser, 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. In addition, when performing exposure of a large area, after forming a photosensitive resin layer on a substrate such as a glass substrate, exposure is performed while transporting, thereby exposing a large area with an exposure machine having a small exposure area. Can do.

  Examples of the exposure light used for exposure include visible light, near ultraviolet light, ultraviolet light, electron beam, X-ray, and laser light. Among these, ultraviolet light is preferable, and the light source includes, for example, Low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, halogen lamp and the like. 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 narrowing the wavelength region of light using a wavelength filter, light scattering can be suppressed and pattern formability 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 resin layer is developed using the difference in solubility in the developer between the exposed portion and the non-exposed portion to form a pattern of the resin 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.) And may be selected and set as appropriate according to the type of the photosensitive resin layer.

  As the developer used in the development step, an organic solvent capable of dissolving the photosensitive resin in the photosensitive resin 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 resin layer, development can be performed with an alkaline aqueous solution.

  In the present invention, the photosensitive resin layer contains inorganic particles. Since the inorganic particles are uniformly dispersed by the alkali-soluble resin (C), the resin (C) is dissolved in a developer and washed. By doing so, inorganic particles are also removed at the same time.

  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 additives such as the above-described nonionic surfactants and organic solvents. 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 resin layer remaining portion (pattern of the resin layer) after the development, the pattern of the resin 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 resin layer formation, exposure, development and firing 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 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.
[Aluminum powder evaluation method]
The 50 wt% particle size (D50) was measured by a laser diffraction method using “SALD-2100” manufactured by Shimadzu Corporation. The average circularity and average length are average values when measuring 3000 arbitrary particles using a particle size / shape distribution measuring instrument “PITA-1” manufactured by Sysmex Corporation.

[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 GPC (“HLC-8220GPC” manufactured by Tosoh Corporation). The GPC measurement was performed under the conditions of a measurement temperature of 40 ° C. using “TSK guard column Super HZM-M” manufactured by Tosoh Corporation as a GPC column and tetrahydrofuran (THF) as a solvent.

[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 "and evaluated according to the following criteria.
A: Volume resistance value is less than 100 μΩ · cm.
○: The volume resistance value is 100 to 200 μΩ · cm.
X: Volume resistance value is larger than 200 μΩ · cm.

[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 evaluation is impossible.

[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.

As a result, cellotape (registered trademark) (manufactured by Nichiban Co., Ltd.) was transferred to the surface of the support and brought into close contact. This cello tape (registered trademark) (manufactured by Nichiban Co., Ltd.) was peeled from the support to evaluate the adhesion between the pattern and the support.
○: No pattern peeling.
X: Pattern peeling occurred.

[Synthesis Example 1]
2-hydroxyethyl methacrylate 15 parts, methacrylic acid 15 parts, n-butyl methacrylate 40 parts, 2-ethylhexyl methacrylate 30 parts, azobisisobutyronitrile (AIBN) 1 part, pentaerythritol tetrakis (3-mercaptopropionic acid) ( 5 parts (manufactured by Sakai Chemical Industry Co., Ltd.) were charged into an autoclave equipped with a stirrer and stirred in 150 parts of terpineol in a nitrogen atmosphere until uniform.

  Next, the monomer was polymerized at 80 ° C. for 4 hours, and the polymerization was further continued at 100 ° C. for 1 hour, followed by cooling to room temperature to obtain an alkali-soluble resin (C1) having an SH group. The polymerization rate of the alkali-soluble resin (C1) was 98%, and the weight-average molecular weight of the alkali-soluble resin (C1) was 21000 (Mw / Mn 1.9).

[Preparation Example 1]
60 parts of alkali-soluble resin (C1) as alkali-soluble resin (C), 35 parts of trimethylolpropane (propylene oxide-modified) triacrylate as polyfunctional (meth) acrylate (D), 2 as photopolymerization initiator (E) -Methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propan-1-one was mixed in an amount of 3.5 parts and 2,4-diethylthioxanthone in an amount of 1.5 parts; Photosensitive resin (1) was prepared. Next, 100 parts of photosensitive resin (1) and 15 parts of terpineol were mixed to prepare a resin solution.

[Example 1]
The total content of aluminum powder (A1) shown in Table 1, glass powder (B1) shown in Table 2, and photosensitive resin (1) shown in Table 3 is 56. Aluminum powder (A1), glass powder (B1) and the above resin so that the content of glass powder (B1) is 0%, the content of photosensitive resin (1) is 30.0% The solution was kneaded with a kneader to prepare a photosensitive paste composition (hereinafter also referred to as “photosensitive paste”).

上記感光性ペーストを、３２５メッシュのスクリーンを用いて試験片であるガラス基板（１５０ｍｍ×１５０ｍｍ×２．８ｍｍ）上に１００ｍｍ角の大きさにベタに印刷し、１００℃で１０分間保持して乾燥して感光性樹脂層を形成した。前記感光性樹脂層の膜厚は、１０μｍ±１μｍの範囲にあった。

The above photosensitive paste is printed on a glass substrate (150 mm × 150 mm × 2.8 mm) as a test piece using a 325 mesh screen in a solid size of 100 mm square, held at 100 ° C. for 10 minutes and dried. Thus, a photosensitive resin layer was formed. The film thickness of the photosensitive resin layer was in the range of 10 μm ± 1 μm.

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

Next, the resin layer was developed by applying a 0.5% aqueous solution of sodium carbonate kept at 23 ° C. to the exposed photosensitive resin layer for 60 seconds in a shower. Then, it washed with water using the shower spray. Thereby, the non-exposed part which was not photocured was removed and the grid | lattice-like 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 16]
In Example 1, a photosensitive resin 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 the photosensitive paste composition was prepared with the composition and ratio shown in Table 4. . The obtained cured pattern and electrode pattern were evaluated according to the above evaluation methods. The results are shown in Table 4.

[Comparative Examples 1 to 11]
In Example 1, a photosensitive resin 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 the photosensitive paste composition was prepared with the composition and ratio shown in Table 5. . The obtained cured pattern and electrode pattern were evaluated according to the above evaluation methods. The results are shown in Table 5.

表４に示すように、実施例１〜１６における現像後の硬化パターンの評価は、何れの実施例においても良好であった。また、焼成後の電極パターンの評価も、何れの実施例においても良好であった。さらに、実施例２、４、７および９における体積抵抗の評価は特に良好であり、その他の実施例における体積抵抗の評価も良好であった。

As shown in Table 4, the evaluation of the cured pattern after development in Examples 1 to 16 was good in any Example. Moreover, the evaluation of the electrode pattern after firing was also good in any of the examples. Furthermore, evaluation of volume resistance in Examples 2, 4, 7 and 9 was particularly good, and evaluation of volume resistance in other Examples was also good.

表５に示すように、比較例１〜１１における体積抵抗の評価では、何れの比較例においても所望の規格を満たすことはできなかった。また、比較例１、３、５、８〜１０における硬化パターンおよび電極パターンの評価では、所望の規格を満たすことはできなかったほか、比較例６、８〜１０における支持体との密着性の評価では、密着性が悪くパターンが剥れてしまった。

As shown in Table 5, in the evaluation of volume resistance in Comparative Examples 1 to 11, the desired standard could not be satisfied in any of the Comparative Examples. Moreover, in the evaluation of the cured pattern and the electrode pattern in Comparative Examples 1, 3, 5, and 8 to 10, the desired standard could not be satisfied, and the adhesion with the support in Comparative Examples 6 and 8 to 10 was not achieved. In the evaluation, the adhesion was poor and the pattern was peeled off.

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 (3)

Aluminum powder (A),
Glass powder (B),
Alkali-soluble resin (C),
Containing a polyfunctional (meth) acrylate (D), and a photopolymerization initiator (E),
The aluminum powder (A) has a 50% by weight particle size (D50) of 0.5 to 20.0 μm, an average circularity of 0.7 or more, and the ratio of the major axis to the minor axis of the powder particle (major axis / minor axis). And the content of the glass powder (B) is from 10 to 30% by weight with respect to the total of 100% by weight of the aluminum powder (A) and the glass powder (B). A photosensitive paste composition.   The aluminum powder (A) with respect to a total of 100% by weight of the aluminum powder (A), glass powder (B), alkali-soluble resin (C), polyfunctional (meth) acrylate (D) and photopolymerization initiator (E) 2. The photosensitive paste composition according to claim 1, wherein the total content of the glass powder (B) is 60 to 80% by weight. Forming a photosensitive resin layer comprising the photosensitive paste composition according to claim 1 or 2 on a substrate;
A step of exposing the resin layer to form a latent image of a pattern;
A pattern forming method comprising: a step of developing the resin layer to form a pattern; and a step of baking the pattern.

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