JP2010276703A - Photosensitive paste composition and pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive paste composition which is inexpensive and enables to form a thin-film, high-definition pattern with a low resistance value on a glass substrate. <P>SOLUTION: The photosensitive paste composition comprises: a conductive component (A) comprising (A1) 30-5 wt.% of aluminum powder and (A2) 70-95 wt.% of at least one selected from aluminum alloy powders and zinc powder; an alkali-soluble resin (C); a polyfunctional (meth)acrylate (D); and a photopolymerization initiator (E). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a photosensitive paste composition and a pattern forming method. For more details,
A photosensitive paste composition capable of forming a high-sensitivity and high-precision pattern when manufacturing a display panel such as a flat panel display, an advanced mounting material for electronic components, and a member of a solar cell, and the composition are used. The present invention relates to a pattern forming method.

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

FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC type PDP. In FIG. 1, 101 and 1
02 is a glass substrate arranged opposite to it, 103 and 111 are partition walls, and the glass substrate 101
The cells are partitioned by 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, and 105 is a transparent electrode 104.
The bus electrode is formed on the transparent electrode 104 for the purpose of lowering the resistance, and 106 is an address electrode fixed to the glass substrate 102. 107 is a fluorescent material held in the cell, 108 is a dielectric layer formed on the surface of the glass substrate 101 so as to cover the transparent electrode 104 and the bus electrode 105, and 109 is used to cover the address electrode 106. A dielectric layer formed on the surface of the glass substrate 102, and 110 is a protective layer made of, for example, magnesium oxide.

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

Therefore, at present, pattern formation by photolithography is mainly used.
For example, when an electrode is manufactured, a large and high-definition pattern can be formed by a photolithography method using a photosensitive silver paste, which is a problem that cannot be dealt with by a screen printing method.

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

As described above, due to the recent demands for pattern accuracy and cost reduction, an inorganic particle-containing photosensitive resin material capable of forming an inexpensive and high-definition pattern on a ceramic, silicon, and glass substrate is desired.
Photosensitive resin materials using aluminum powder have been studied as an inexpensive material to replace silver. (Japanese Patent Laid-Open No. 2009-37232)
JP 2009-37232 A

    However, in the photosensitive paste composition disclosed in JP-A-2009-3722, it has been desired that an electrode having a lower resistance value can be obtained although the molded electrode has adhesion to the substrate.

The present invention seeks to solve the problems associated with the prior art as described above. That is, an object of the present invention is to provide a photosensitive paste composition that is inexpensive, thin, has a low resistance value, and can form a high-definition pattern on a glass substrate. 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, the inventors have found that the above-mentioned problems can be solved by using aluminum powder and aluminum alloy and / or zinc powder as an aluminum component at a certain ratio, and have completed the present invention.
That is, the present invention
(1) (A1) A conductive component containing 30 to 5% by weight of the total conductive component of aluminum powder and (A2) 70 to 95% by weight of the total conductive component of at least one selected from aluminum alloy powder and zinc powder ( A),
A photosensitive paste composition comprising an alkali-soluble resin (C), a polyfunctional (meth) acrylate (D) and a photopolymerization initiator (E), and a photosensitive paste layer comprising the photosensitive paste composition A step of forming a latent image of the pattern by exposing the paste layer to exposure, a step of forming the pattern by developing the paste layer, and a step of baking the pattern. And a pattern forming method characterized by the above.

According to the present invention, there is provided a photosensitive paste composition that can form a high-definition pattern on a glass substrate or silicon substrate that is inexpensive, thin, has low resistance, and has good adhesion to a support. The Moreover, according to this invention, the pattern formation method using the said photosensitive paste composition is provided.

In particular, by using the photosensitive paste composition according to the present invention, an inexpensive and high-definition pattern can be formed, formation of members constituting FPD wiring, formation of members for highly mounting materials for electronic components And suitable for forming solar cell members.

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

[Photosensitive paste composition]
The photosensitive paste composition according to the present invention contains a conductive component (A), an alkali-soluble resin (C), a polyfunctional (meth) acrylate (D) and a photopolymerization initiator (E) described below. Moreover, you may mix | blend glass powder (B) and an additive with the said photosensitive paste composition.

<Conductive component (A)>
<Aluminum powder (A1)>
Examples of the aluminum powder (A1) include flaky aluminum powder and spherical aluminum powder.
The flaky aluminum powder has a 50 wt% particle size (hereinafter also referred to as “D50”) of 2.0 to 20 μm and an average thickness of 0.1 to 1 μm; preferably D50 of 2.5 to 18 μm and an average The thickness is 0.15 to 0.9 μm; more preferably, D50 is in the range of 3.0 to 15 μm and the average thickness is in the range of 0.15 to 0.8 μm.

When D50 or flaky aluminum powder having an average thickness exceeding the above range is used, it may be difficult to form a high-definition pattern. Also, when D50 or flaky aluminum powder having an average thickness lower than the above range is used, the powders tend to have point contact rather than surface contact in the film, so it is difficult to form a low resistance pattern. May be.

In the present invention, the 50% by weight particle diameter (D50) is a value when measured by the laser diffraction method under the measurement conditions in Examples described later. The average thickness is a value when measured under SEM observation under the measurement conditions in the examples described later.

The flaky aluminum powder is not particularly limited as long as the flaky aluminum powder satisfies the above requirements (D50 and average thickness). Examples of the flaky aluminum powder include the flaky powder clathrated with a fatty acid.
For example, when the electrode constituting the wiring of the FPD is formed, the above-described flaky aluminum powder is preferably used. In particular, the leafing value measured according to the method described in JIS K 5906 is small (or the leafing value). Non-leafing flaky aluminum powder is preferably used. Moreover, the said flaky aluminum powder of the said illustration may be used individually by 1 type, and may use 2 or more types together.

Examples of the fatty acid include butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid,
Pelargonic acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, palmitoyl acid, margaric acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, nonadecanoic acid, arachidic acid, arachidonic acid, behenic acid, lignoselenic acid, nerbon Acid, serotic acid,
Examples include montanic acid and melicic acid. Among these fatty acids, oleic acid can efficiently include and / or modify aluminum powder. By inclusion and / or modification of the flaky aluminum powder using a fatty acid such as oleic acid, a non-leafing flaky aluminum powder can be easily obtained. By using such non-leafing flaky aluminum powder, it becomes possible to more uniformly disperse the aluminum powder in the photosensitive paste layer. For this reason, the photosensitive paste layer obtained in this way can be satisfactorily patterned without reflecting exposure light (that is, the transmittance is improved).

  The spherical aluminum powder has a 50% by weight particle size (D50) in the range of 1 to 20 μm, preferably 1.5 to 18 μm, more preferably 2 to 15 μm. In the present invention, the shape of the spherical aluminum powder means a shape other than flakes (flakes) and is not particularly limited.

When spherical aluminum powder having a D50 exceeding the above range is used, it may be difficult to form a high-definition pattern. In addition, when spherical aluminum powder having a D50 lower than the above range is used, the yield may be poor and it may be difficult to form a pattern at a low cost.

<Aluminum alloy powder and zinc powder (A2)>
The aluminum alloy powder that can be used in the present invention has a 50% by weight particle diameter (D50) of 1 to 20 μm, preferably 1 to 15 μm, particularly preferably 1 to 10 μm.
The aluminum alloy powder used in the present invention contains aluminum and at least one selected from zinc, indium, titanium, bismuth, silicon, copper, lanthanoid, manganese, and magnesium. In particular, an aluminum alloy powder containing zinc is preferable, and the zinc content in the aluminum alloy powder is 5 to 97% by weight.
By using an aluminum alloy powder containing zinc in this proportion, a photosensitive paste composition excellent in terms of adhesion and electrical characteristics of the coating film after firing can be obtained.
The aluminum content in the aluminum alloy powder is 1 to 60% by weight, preferably 1 to 50% by weight.
Examples of the zinc powder component (A3) used in the present invention include flaky zinc powder and spherical zinc powder.
The flaky zinc powder has a 50% by weight particle diameter (hereinafter also referred to as “D50”) of 2.0 to 20 μm and an average thickness of 0.1 to 1 μm; preferably D50 of 2.5 to 18 μm and an average The thickness is 0.15 to 0.9 μm; more preferably, D50 is in the range of 3.0 to 15 μm and the average thickness is in the range of 0.15 to 0.8 μm.

  When D50 or flaky zinc powder having an average thickness exceeding the above range is used, it may be difficult to form a high-definition pattern. Further, when D50 or flaky zinc powder having an average thickness lower than the above range is used, it is difficult to form a low resistance pattern because the powders tend to be point contact rather than surface contact in the film. May become.

In the present invention, the 50% by weight particle diameter (D50) is a value when measured by the laser diffraction method under the measurement conditions in Examples described later. The average thickness is a value when measured under SEM observation under the measurement conditions in the examples described later.

The flaky zinc powder is not particularly limited as long as the flaky zinc powder satisfies the above requirements (D50 and average thickness). Examples of the flaky zinc powder include the flaky powder clathrated with a fatty acid.
For example, when forming an electrode constituting an FPD wiring, the flaky powder exemplified above is preferably used. In particular, the leafing value measured according to the method described in JIS K 5906 is small (or the leafing value is small). A non-leafing flaky powder is preferably used. Moreover, the said flake shaped powder of the said illustration may be used individually by 1 type, and may use 2 or more types together.

Examples of the fatty acid include butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid,
Pelargonic acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, palmitoyl acid, margaric acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, nonadecanoic acid, arachidic acid, arachidonic acid, behenic acid, lignoselenic acid, nerbon Acid, serotic acid,
Examples include montanic acid and melicic acid. Among these fatty acids, oleic acid can efficiently include and / or modify aluminum powder. By inclusion and / or modification of the flaky powder using a fatty acid such as oleic acid, a non-leafing flaky powder can be easily obtained. By using such non-leafing flaky zinc powder, the zinc powder can be more uniformly dispersed in the photosensitive paste layer. For this reason, the photosensitive paste layer obtained in this way can be satisfactorily patterned without reflecting exposure light (that is, the transmittance is improved).

  The spherical zinc powder has a 50 wt% particle size (D50) in the range of 1 to 20 µm, preferably 1.5 to 18 µm, more preferably 2 to 15 µm. In the present invention, the shape of the spherical zinc powder means a shape other than flakes (flakes) and is not particularly limited.

When spherical zinc powder having a D50 exceeding the above range is used, it may be difficult to form a high-definition pattern. Moreover, when the spherical zinc powder whose D50 is less than the above range is used, the yield may be poor and it may be difficult to form a pattern at a low cost.
<Constitution ratio of conductive component>
The content of aluminum powder (A1) in the conductive component is 5 to 30% by weight, preferably 10 to 30% by weight, and the content of aluminum alloy powder and / or zinc powder is 70 to 95% by weight, preferably 70 to 90%. % By weight.
In the photosensitive paste composition according to the present invention, the content of the conductive component (A) is preferably 10 to 60% by weight, more preferably 15 to 50% by weight, still more preferably, based on the entire composition of the present invention. Is in the range of 20-40% by weight. When content of an electroconductive component (A) exists in the said range, the pattern excellent in electroconductivity can be formed.

<Glass powder (B)>
In the present invention, it is preferable to use glass powder (B). A glass powder (B) can be suitably selected according to the use (for example, member of FPD, member of electronic components, etc.) of the pattern formed using the photosensitive paste composition which concerns on this invention.

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

The average particle diameter of the glass powder (B) is appropriately selected in consideration of the pattern shape. The 50% by weight particle size (D50) of the glass powder (B) is preferably in the range of 0.2 to 5 μm, more preferably 0.2 to 4 μm, and still more preferably 0.5 to 3.8 μm. Moreover, it is preferable that the 10 weight% particle diameter (D10) of glass powder (B) exists in the range of 0.05-0.5 micrometer, and a 90 weight% particle diameter (D90) exists in the range of 10-20 micrometers. preferable. When the average particle diameter (D50, D10, D90) of the glass powder (B) is in the above range, the exposure light sufficiently reaches the bottom of the photosensitive paste layer in the exposure step, and a high-definition pattern can be formed. it can.

In the present invention, the 50 wt% particle size (D50), 10 wt% particle size (D10), and 90 wt% particle size (D90) are measured by the laser diffraction method under the measurement conditions in the examples described later. This is the value when

For example, when forming an electrode constituting an FPD wiring, as the glass powder (B), (B1) a glass powder having a softening point of preferably 350 to 700 ° C., more preferably 400 to 620 ° C. (Hereinafter also referred to as “glass powder (B1)”) is preferably used.

When glass powder having a softening point lower than the above range is used, the organic paste such as the alkali-soluble resin (C) is not completely decomposed and removed in the step of baking the pattern formed by exposing and developing the photosensitive paste layer. Since the glass powder melts, a part of the organic substance may remain in the electrode. As a result, the electrode may be colored and its light transmittance may be reduced. On the other hand, if a glass powder with a softening point exceeding the above range is used, the temperature condition becomes very high in the process of baking the pattern formed by exposing and developing the photosensitive paste layer, so that the glass substrate is distorted. May occur.

In the present invention, the softening point of the glass powder (B) is a value when measured by DSC measurement under measurement conditions in Examples described later.
In the photosensitive paste composition according to the present invention, the content of the glass powder (B) is preferably 0.5 to 35% by weight, more preferably 1 to 25% by weight, and still more preferably based on the entire composition. Is in the range of 1.5 to 20% by weight.

  In particular, it is preferable that at least a part of the glass powder (B) is the glass powder (B1), and the content of the glass powder (B1) is preferably 1 to 25 weights with respect to the entire photosensitive paste composition. %, More preferably in the range of 1.5 to 20% by weight. When the content of the glass powder (B1) is in the above range, it is suitable for forming a member such as an electrode constituting the FPD wiring.

<Alkali-soluble resin (C)>
The alkali-soluble resin (C) 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 desired development processing can be performed.

Examples of the alkali-soluble resin (C) include the following alkali-soluble functional group-containing monomers (C1
) And a (meth) acrylic acid derivative (C2).
<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, succinic acid mono (2- (meth) acryloyloxyethyl), 2-methacryloyloxyethylphthalic acid, 2-acryloyloxy Carboxyl group-containing monomers such as ethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2-acryloyloxypropyl tetrahydrohydrogen phthalate, and 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.

These monomers (C1) may be used individually by 1 type, and may use 2 or more types together. Among these monomers (C1), (meth) acrylic acid, 2-methacryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydro Hydrogen phthalate, 2-acryloyloxypropyl tetrahydrohydrogen phthalate, 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 in all the structural units of the alkali-soluble resin (C).
, Preferably 10 to 80% by weight, more preferably 15 to 70% by weight.

<(Meth) acrylic acid derivative (C2)>
As the (meth) acrylic acid derivative (C2), an alkali-soluble functional group-containing monomer (C
Any (meth) acrylic acid derivative copolymerizable with 1) is not particularly limited. 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, phenoxyethyl (meth) acrylate, trityl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate, etc. of,
Examples include (meth) acrylates other than the monomer (C1).

These monomers (C2) may be used individually by 1 type, and may use 2 or more types together.
In the present invention, instead of the (meth) acrylic acid derivative (C2), or (meth)
Along with the acrylic acid derivative (C2), for example, styrene, methyl (meth) acrylate,
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 ethyl (meth) acrylate, 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.

Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile,
2'-azobis (2-methylbutylnitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 1,1'-azobis (1-cyclohexanecarbonitrile), dimethyl-2,2'-azo Azo compounds such as bisisobutyrate and 4,4′-azobis (4-cyanovaleric acid); t-butyl peroxybivalate, t-butylperoxy 2-ethylhexanoate, cumylperoxy 2-ethylhexanoate Organic peroxides of peroxyesters such as ate.

These radical polymerization initiators may be used alone or in combination of two or more.
The amount of these radical polymerization initiators used is 100% of all monomers used for the copolymerization.
Usually, it is about 0.1 to 10 parts by weight with respect to parts by weight.

<Chain transfer agent>
In the copolymerization, a chain transfer agent may be used. Examples of the chain transfer agent include α-methylstyrene dimer, t-dodecyl mercaptan, pentaerythritol tetrakis (3
-Mercaptopropionic acid), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane.

These chain transfer agents may be used individually by 1 type, and may use 2 or more types together. Further, the amount of these chain transfer agents used is based on 100 parts by weight of the total monomers used for the copolymerization.
Usually, it is about 0.1 to 10 parts by weight.

<Physical properties of alkali-soluble resin (C)>
The weight average molecular weight (hereinafter also referred to as “Mw”) of the alkali-soluble resin (C) is a polystyrene conversion value measured by gel permeation chromatography (GPC), preferably 5,000 to 100,000, more preferably 10,000 to 80000. is there. Mw can be controlled by appropriately selecting conditions such as a copolymerization ratio of the monomer, a chain transfer agent, and a polymerization temperature. If Mw exceeds the above range, film roughness after development tends to occur. On the other hand, if Mw is less than the above range, the solubility of the unexposed portion in the developer may be reduced, and the pattern resolution may be reduced.

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

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

The photosensitive paste composition according to the present invention comprises 5 to 90% by weight (5 to 89.5% by weight) of a photosensitive resin component and 95 to 10% by weight (95 to 10.5% by weight) of inorganic particles. It is preferable to become. The photosensitive resin component is a portion obtained by removing inorganic particles from the photosensitive paste composition,
That is, it refers to the entire organic component having a photosensitive function, such as alkali-soluble resin (C), polyfunctional (
A (meth) acrylate (D), a photoinitiator (E), etc. are contained. The inorganic particles include aluminum powder (A) such as flaky aluminum powder (A1) and spherical aluminum powder (A2), glass powder (B), and the like.

<Multifunctional (meth) acrylate (D)>
The photosensitive paste composition according to the present invention contains a photosensitive component. As the photosensitive component, there are generally a light-insolubilized component and a light-solubilized component.

Examples of the photoinsolubilized component include (i) a photosensitive monomer or oligomer having one or more unsaturated groups in the molecule, (ii) a photosensitive compound such as an aromatic diazo compound, an aromatic azide compound, or an organic halogen compound. (Iii) There are so-called diazo resins such as a condensate of diazo amine and formaldehyde.

Examples of the light-solubilizing component include (iv) a complex of a diazo compound and an inorganic acid or an organic acid, (v)
Quinonediazos, (vi) those obtained by binding quinonediazos to a suitable polymer binder (for example, naphthoquinone-1,2-diazide-5-sulfonic acid ester of phenol resin), and the like.

In the present invention, all of the above components can be used, but in terms of being easily used by mixing with the above inorganic particles, the polyfunctionality (classified as the above (i) photosensitive monomer or oligomer). (Meth) acrylate (D) is used as an essential component.

Examples of the polyfunctional (meth) acrylate (D) include allylated cyclohexyl di (meth) acrylate, 2,5-hexanedi (meth) acrylate, 1,3-butanediol di (meth) acrylate, and 1,4-butane. Diol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth)
Acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, Di (meth) taacrylates such as methoxylated cyclohexyl di (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, triglycerol di (meth) acrylate;
Pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane PO-modified tri (meth) acrylate, trimethylolpropane EO-modified tri (meth) acrylate, benzyl mercaptan (meth) triacrylate, ditrimethylolpropane Tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (
Tri- or more functional (meth) acrylates such as (meth) acrylate;
Among the hydrogen atoms bonded to the aromatic ring in the above compound, there may be mentioned monomers in which 1 to 5 are substituted with chlorine atoms or bromine atoms. These polyfunctional (meth) acrylates (D) may be used alone or in combination of two or more.

In the photosensitive paste composition according to the present invention, the content of the polyfunctional (meth) acrylate (D) is preferably 1 with respect to the entire photosensitive resin component from the viewpoint of sensitivity to exposure light.
It is 0 weight% or more, More preferably, it exists in the range of 15-60 weight%. When content of polyfunctional (meth) acrylate (D) exceeds the said range, the shape of the member after baking (for example, member for display panels) may deteriorate.

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

<Photopolymerization initiator (E)>
A conventionally well-known photoinitiator can be used as a photoinitiator (E). Also,
In order to improve the exposure sensitivity, a sensitizer may be used together with the photopolymerization initiator (E).

Examples of the photopolymerization initiator (E) include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, and 4,4-bis (diethylamino).
Benzophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2
, 2-Dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-
Methylpropiophenone, pt-butyldichloroacetophenone, thioxanthone, 2
-Methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 2,4
-Diethylthioxanthone, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methyleneanthrone, 4-azidobenzalacetophenone 2,6-bis (p-azidobenzylidene) cyclohexanone, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, camphorquinone, 2-phenyl-1,2-butadion-2- (o-methoxy) Carbonyl) oxime, 1-phenyl-propanedione-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl 3-ethoxy - propan trione 2- (o-benzoyl) oxime, Michler's ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-
Morpholino-1-propan-1-one, 2-benzyl-2-dimethylamino-1- (4
-Morpholinophenyl) butanone-1,2-hydroxy-2-methyl-1-phenyl-
Carbonyl compounds such as 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) -phenyl Acylphosphine oxide compounds such as phosphine oxide;
Benzyldimethylketanol, benzylmethoxyethyl acetal, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, 4,4
-Azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, carbon tetrabrominated, tribromophenylsulfone, benzoin peroxide;
A combination of a photoreducible pigment such as eosin or methylene blue and a reducing agent such as ascorbic acid or triethanolamine can be mentioned. These photoinitiators (E) may be used individually by 1 type, and may use 2 or more types together.

In the photosensitive paste composition according to the present invention, the content of the photopolymerization initiator (E) is preferably 1 to 50 parts by weight, more preferably 100 parts by weight of the polyfunctional (meth) acrylate (D). It is in the range of 2 to 40 parts by weight. When content of a photoinitiator (E) exceeds the said range, the shape of the member after baking (for example, member for display panels) may deteriorate.

<Sensitizer>
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-dimethyla Minibenzal) 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-dimethylaminophenylvinylene) -isonaphthothiazole, 1,3-bis (4-
Dimethylaminobenzal) acetone, 1,3-carbonyl-bis (4-diethylaminobenzal) acetone, 3,3-carbonyl-bis (7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N-phenyl Ethanolamine, N-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate,
Isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole,
An example is 1-phenyl-5-ethoxycarbonylthiotetrazole.

These sensitizers may be used alone or in combination of two or more. Some sensitizers are also used as photopolymerization initiators, and the combination with the photopolymerization initiator determines whether it is a sensitizer or a photopolymerization initiator.

In the photosensitive paste composition according to the present invention, the content of the sensitizer is the inorganic particles 100 described above.
Preferably it is 0.01-5 weight part with respect to a weight part, More preferably, it exists in the range of 0.05-3 weight part. When the content of the sensitizer is less than the above range, the effect of improving the photosensitivity may not be exhibited. When the content of the sensitizer exceeds the above range, the residual ratio of the exposed portion may become too small. is there.

<Additives>
The photosensitive paste composition according to the present invention includes an ultraviolet absorber, a polymerization inhibitor, an antioxidant, an organic solvent, an adhesion assistant, a dissolution accelerator, a sensitizer, a plasticizer, a thickener, a dispersant, Additives such as inorganic particles and alkali-soluble resin anti-settling agents and leveling agents may be added.

<Ultraviolet absorber>
You may add a ultraviolet absorber to the photosensitive paste composition which concerns on this 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, an organic dye or an inorganic pigment can be used, and among them, an organic dye or an inorganic pigment having a high ultraviolet absorption coefficient in a wavelength range of 350 to 450 nm is preferably used.

Examples of organic dyes include azo dyes, amino ketone dyes, xanthene dyes,
Quinoline dyes, amino ketone dyes, anthraquinone dyes, benzophenone dyes,
Examples include diphenyl cyanoacrylate dyes, triazine dyes, and p-aminobenzoic acid dyes; examples of inorganic pigments include zinc oxide, titanium oxide, and cerium oxide. Among these, when forming an electrode constituting an FPD wiring, an inorganic pigment such as zinc oxide, titanium oxide, cerium oxide or the like is more preferable from the viewpoint of 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). When the addition amount of the inorganic pigment is less than the above range, the effect of adding the ultraviolet absorber is small and the desired effect may not be obtained. In addition, if the amount of inorganic pigment added exceeds the above range, the effect of adding an ultraviolet absorber is great, and exposure light does not reach the bottom of the photosensitive paste layer, making it impossible to form a pattern and maintaining film strength. There may not be.

<Polymerization inhibitor>
In order to improve the thermal stability during storage, a polymerization inhibitor may be added to the photosensitive paste composition according to the present invention. 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 is preferably 0.001 to 1% by weight based on the entire photosensitive paste composition.
Can be added in an amount in the range of.
<Antioxidant>
In order to prevent oxidation of the alkali-soluble resin (C) during storage, an antioxidant may be added to the photosensitive paste composition according to the present invention. Examples of the antioxidant include 2, 6
-Di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-
4-ethylphenol, 2,2-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2-methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4
-Bis- (3-methyl-6-tert-butylphenol), 1,1,3-tris- (2-methyl-6-tert-butylphenol), 1,1,3-tris- (2-methyl-4- Hydroxy-t-butylphenyl) butane, bis [3,3-bis- (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, dilaurylthiodipropionate, triphenyl phosphite. .

The antioxidant is preferably 0.001 to 1% by weight based on the entire photosensitive paste composition.
Can be added in an amount in the range of.
<Organic solvent>
An organic solvent may be added to the photosensitive paste composition according to the present invention in order to adjust its viscosity. 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 , Dibromobenzene, dichlorobenzene, bromobenzoic acid, and chlorobenzoic acid. These organic solvents may be used individually by 1 type, and may use 2 or more types together.

The organic solvent can be added in an amount that is preferably in the range of 15 to 40% by weight with respect to the entire photosensitive paste composition.
<Adhesion aid>
An adhesion assistant may be added to the photosensitive paste composition according to 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 having a reactive group such as γ-methacryloxypropyltrimethoxysilane is preferably used.

In the photosensitive paste composition according to the present invention, the content of the adhesion assistant is preferably 0.05 to 15 parts by weight, more preferably 0.00 with respect to 100 parts by weight of the alkali-soluble resin (C).
It is in the range of 1 to 10 parts by weight.

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

Examples of commercially available fluorosurfactants include “BM-10” manufactured by BM CHIMIE.
00 ”,“ BM-1100 ”;“ MegaFuck F142D ”manufactured by Dainippon Ink & Chemicals, Inc.
”,“ F172 ”,“ 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”
“Same S-141”, “Same S-145”, “Same S-382”, “Same SC-101”, “Same S
C-102 "," SC-103 "," SC-104 "," SC-105 "," S
C-106 ".

Examples of commercially available silicone surfactants include “SH-28PA”, “SH-190”, “SH-193”, and “SZ-603” manufactured by Toray Dow Corning Silicone Co., Ltd.
2 ”,“ SF-8428 ”,“ DC-57 ”,“ DC-190 ”;“ KP341 ”manufactured by Shin-Etsu Chemical Co., Ltd .;“ F-top EF301 ”,“ same EF303 ”manufactured by Shin-Akita Chemical Co., Ltd. "
EF352 ”.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene distyrenated phenyl ether,
Polyoxyethylene aryl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyoxyethylene dilaurate;
And polyoxyethylene dialkyl esters such as polyoxyethylene distearate.

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

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

Among these surfactants, non-ionic surfactants are preferable, polyoxyethylene aryl ethers are more preferable, and polyoxyethylene aryl ethers are more preferable because unexposed portions can be easily removed during development. Then, the compound represented by the following formula (1) is particularly preferable.

In the above formula (1), R1 is an alkyl group having 1 to 5 carbon atoms, preferably a methyl group;
S is an integer of 1 to 5, preferably 2, and t is an integer of 1 to 100, preferably 10 to 20.

In the photosensitive paste composition according to 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 in the range of 0.1 to 10 parts by weight. When the content of the dissolution accelerator is in the above range, a photosensitive paste composition having excellent solubility in a developer described later can be obtained.

<Preparation of photosensitive paste composition>
The photosensitive paste composition according to the present invention comprises a conductive component (A) containing an aluminum powder (A1) and an aluminum alloy powder, an alkali-soluble resin (C), a polyfunctional (meth) acrylate (D) and a photopolymerization initiator ( E), glass powder (B), and an additive such as an organic solvent are prepared so as to have a predetermined composition ratio, and then mixed and dispersed homogeneously with a three roll or kneader.

The viscosity of the photosensitive paste composition according to the present invention can be adjusted as appropriate according to the amount of the inorganic particles, thickener, organic solvent, plasticizer, precipitation inhibitor, and the like.
It is preferably in the range of 000 cps (centipoise).

The photosensitive paste composition is a photosensitive paste layer obtained in a step of forming a photosensitive paste layer made of the photosensitive paste composition on a substrate (photosensitive paste layer forming step), and has a film thickness of 5 μm and a wavelength of 365 nm. It is preferable that the transmittance with respect to light becomes 0.1% or more. When the transmittance for light having a wavelength of 365 nm with a film thickness of 5 μm is less than 0.1%, pattern formation by a photolithography method may be difficult.

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

<Photosensitive paste layer forming step>
In this step, a photosensitive paste layer made of the photosensitive paste composition is formed on the substrate. Examples of the method for forming the photosensitive paste layer include: (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 the drying conditions of a coating film suitably so that the residual ratio of the organic solvent after drying may be within 2 weight%, for example, drying temperature is 50-150 degreeC, and drying time is about 0.5 to 60 minutes. It is.

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

(Ii) An example of the transfer process using the transfer film having the photosensitive paste layer is shown below. The substrate and the transfer film are overlapped so that the substrate and the photosensitive paste layer are in contact, 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 onto and in close contact with 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 polyesters such as polyethylene terephthalate, polyethylene, polypropylene, polystyrene,
Examples include fluorine-containing resins such as polyimide, polyvinyl alcohol, polyvinyl chloride, and polyfluoroethylene, 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.
It is.

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

<Exposure process>
In this step, after forming the photosensitive paste layer on the substrate by the photosensitive paste layer forming step, exposure is performed using an exposure apparatus. Specifically, the photosensitive paste layer is selectively irradiated with exposure light 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. Although the exposure pattern of a photomask changes with purposes, it is a stripe or a grating | lattice of 10-500 micrometers width, for example.

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 exposure light include visible light, near ultraviolet light, ultraviolet light, electron beam, X-ray, and laser light. Among these, ultraviolet light is preferable. Examples of the ultraviolet light source include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, and a halogen lamp. Among these, an ultra high pressure mercury lamp is preferable.

Although exposure conditions vary depending on the coating thickness, for example, exposure is performed for 0.05 to 1 minute using an ultrahigh pressure mercury lamp with an output of 1 to 100 mW / cm <2>. In this case, by using a wavelength filter to narrow the wavelength region of the exposure light, light scattering can be suppressed and pattern formation can be improved. Specifically, a filter that cuts off i-line (365 nm) light, or
Pattern formation can be improved by using a filter that cuts off i-line and h-line (405 nm) light.

<Development process>
In this step, after the exposure, using the difference in solubility in the developer between the exposed part and the non-exposed part,
The photosensitive paste layer is developed to form a pattern. Development method (for example, immersion method, rocking method,
Shower method, spray method, paddle method, brush method, etc.) and development processing conditions (for example, developer type / composition / concentration, development time, development temperature, etc.) are appropriately selected according to the type of photosensitive paste layer. , You can set.

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

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

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

The alkali concentration of the aqueous alkali solution is usually 0.01 to 10% by weight, preferably 0.
1 to 5% by weight. If the alkali concentration is too low, the soluble portion (unexposed portion) is not removed, and if the alkali concentration is too high, the pattern may be peeled off or the non-soluble portion (exposed 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 nonionic surfactants and organic solvents. In addition, after the development process with an alkali developer, a washing process is usually performed.

<Baking process>
In this step, the pattern is baked in a baking furnace in order to burn off organic substances contained in the pattern formed in the development step.

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

Since the baking treatment conditions require that the organic material in the pattern be burned off,
The firing temperature is 300 to 1000 ° C., and the firing time is about 10 to 90 minutes. For example, when a pattern is formed on a glass substrate, the firing temperature is 350 to 600 ° C., and the firing time is 10 to 6
It is about 0 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.

[Manufacture of FPD materials]
By using the pattern forming method according to the present invention including the above steps, members (electrodes, etc.) constituting the wiring of a display panel (FPD, etc.), members of advanced mounting materials for electronic components (
Circuit pattern and the like) and members of the solar cell member (wiring pattern and the like) can be formed. In particular, an FPD such as a PDP can be obtained by using the pattern forming method according to the present invention.
Can be suitably manufactured.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited at all by these Examples. In the examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, unless otherwise specified.
First, a method for measuring and evaluating physical properties will be described.
[Method for Measuring Weight Average Molecular Weight (Mw) and Weight Average Molecular Weight (Mw) / Number Average Molecular Weight (Mn) (hereinafter referred to as Mw / Mn)]
Mw and Mw / Mn are values in terms of polystyrene measured by gel permeation chromatography (GPC) (“HLC-8220GPC” manufactured by Tosoh Corporation). The GPC measurement was performed using “TSK guard column Super HZM-M” manufactured by Tosoh Corporation as a GPC column under the conditions of a tetrahydrofuran (THF) solvent and a measurement temperature of 40 ° C.
[Evaluation method of electrical resistance measurement]
The volume resistance [μΩ · cm] is obtained by applying a photosensitive paste composition on a glass substrate and baking it to form a 10 μm-thick film on the glass substrate, and the “Resistivity Processor Model Σ manufactured by NPS” -5 ".
[Method for evaluating pattern after development and baking]
The developed and fired test pieces were cut, the pattern cut surface was observed with a scanning electron microscope (“S4200” manufactured by Hitachi, Ltd.), the pattern width and height were measured, and each was evaluated according to the following criteria. . The desired standard is a pattern width of 50 μm, a height of 10 μm, and an interval of 100 μm.
A: The desired standard.
B: Within ± 5% of desired standard.
C: A value exceeding ± 5% and within ± 10% from a desired standard.
D: More than ± 10% from the desired standard.

[Evaluation of pattern adhesion after firing]
Evaluation of adhesion between the pattern and the glass substrate as the support was performed on the test piece after firing as follows. The desired standard is a pattern width of 50 μm, a height of 10 μm, and an interval of 100 μm.
Cello tape (registered trademark: manufactured by Nichiban Co., Ltd.) was thermocompression bonded to the surface of the support constituting the test piece with a heating roller. The pressure bonding conditions were such that the surface temperature of the heating roller was 23 ° C., the roll pressure was 4 kg / cm 2, and the moving speed of the heating roller was 0.5 m / min. As a result, cellophane tape (registered trademark: manufactured by Nichiban Co., Ltd.) was transferred to the surface of the support and brought into close contact. The adhesiveness of the pattern was evaluated by peeling this cello tape (registered trademark: manufactured by Nichiban Co., Ltd.) from the support.
○: No pattern peeling.
X: Pattern peeling occurred.

[Synthesis Example 1]
2-hydroxyethyl methacrylate 15 g, methacrylic acid 15 g, n-butyl methacrylate 40 g, 2-ethylhexyl methacrylate 30 g, azobisisobutyronitrile (AIBN) 1 g, pentaerythritol tetrakis (3-mercaptopropionate) (Sakai Chemical Industry ( 1 g) was charged into an autoclave equipped with a stirrer, and stirred under a nitrogen atmosphere until uniform in 150 g of dihydroterpineol.
Next, the monomer was polymerized at 80 ° C. for 4 hours, and further polymerized at 100 ° C. for 1 hour, and then cooled to room temperature to obtain an alkali-soluble resin (1). The polymerization rate of this alkali-soluble resin (1) was 98%, and the weight-average molecular weight of the alkali-soluble resin (1) was 20000 (Mw / Mn = 1.6).

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

[Preparation of photosensitive resin component]
Photosensitive resin components (1) to (6) having the compositions shown in Table 3 were prepared.
[Example 1]
Aluminum powder A1-1 (10 g) shown in Table 1, aluminum alloy powder A2-1 (30 g) shown in Table 2, glass powder B1 (5 g) shown in Table 3, and photosensitive resin component (1) shown in Table 4 ( 55 g) was kneaded with a kneader to prepare a photosensitive paste composition (hereinafter also referred to as “photosensitive paste”).
Using a 325 mesh screen, the photosensitive paste is printed on a glass substrate, which is a test piece (150 mm × 150 mm × 1.8 mm), in a solid size of 100 mm square, held at 100 ° C. for 10 minutes and dried. Then, a photosensitive paste layer was formed.
Next, using a negative chrome mask (pattern width 100 μm, pattern interval 100 μm), the photosensitive paste layer was exposed to ultraviolet light from the upper surface with an ultrahigh pressure mercury lamp having an output of 25 mW / cm 2. The exposure amount was 1000 mJ / cm2.
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 5.

[Examples 2 to 27]
Table 5 shows the aluminum powder (10 g) shown in Table 1, the aluminum alloy powder or zinc powder (30 g) shown in Table 2, the glass powder (5 g) shown in Table 3, and the photosensitive resin component (55 g) shown in Table 4. A photosensitive paste layer, a cured pattern, and an electrode pattern were sequentially formed on a glass substrate in the same manner as in Example 1 except that a photosensitive paste was prepared using the combination. Next, the cured pattern and the electrode pattern were evaluated by the above evaluation method. The results are shown in Tables 5 and 6. In any of Examples 2 to 27, the film thickness of the photosensitive paste layer was in the range of 10 μm ± 1 μm.
[Example 28]
Aluminum powder A1-2 (2 g) shown in Table 1, zinc powder A2-20 (38 g) shown in Table 2, glass powder B2 (5 g) shown in Table 3, and photosensitive resin component (1) shown in Table 4 (55 g) ) With a kneader to prepare a photosensitive paste composition (hereinafter also referred to as “photosensitive paste”), in the same manner as in Example 1, the photosensitive paste layer and the cured pattern on the glass substrate. The electrode pattern was sequentially formed. Next, the cured pattern and the electrode pattern were evaluated by the above evaluation method. The results are shown in Table 6. The film thickness of the photosensitive paste layer was in the range of 10 μm ± 1 μm.
[Example 29]
Aluminum powder A1-2 (8 g) shown in Table 1, zinc powder A2-20 (32 g) shown in Table 2, glass powder B2 (5 g) shown in Table 3, and photosensitive resin component (1) shown in Table 4 (55 g) ) With a kneader to prepare a photosensitive paste composition (hereinafter also referred to as “photosensitive paste”), in the same manner as in Example 1, the photosensitive paste layer and the cured pattern on the glass substrate. The electrode pattern was sequentially formed. Next, the cured pattern and the electrode pattern were evaluated by the above evaluation method. The results are shown in Table 6. The film thickness of the photosensitive paste layer was in the range of 10 μm ± 1 μm.
[Example 30]
Aluminum powder A1-2 (12 g) shown in Table 1, zinc powder A2-20 (28 g) shown in Table 2, glass powder B2 (5 g) shown in Table 3, and photosensitive resin component (1) shown in Table 4 (55 g) ) With a kneader to prepare a photosensitive paste composition (hereinafter also referred to as “photosensitive paste”), in the same manner as in Example 1, the photosensitive paste layer and the cured pattern on the glass substrate. The electrode pattern was sequentially formed. Next, the cured pattern and the electrode pattern were evaluated by the above evaluation method. The results are shown in Table 6. The film thickness of the photosensitive paste layer was in the range of 10 μm ± 1 μm.
[Example 31]
Aluminum powder A1-2 (5 g) shown in Table 1, aluminum alloy powder A2-1 (10 g) and zinc powder A2-20 (25 g) shown in Table 2, glass powder B2 (5 g) shown in Table 3, and Table 4 The photosensitive resin component (1) (55 g) shown was kneaded with a kneader to prepare a photosensitive paste composition (hereinafter also referred to as “photosensitive paste”) in the same manner as in Example 1, except that glass A photosensitive paste layer, a cured pattern, and an electrode pattern were sequentially formed on the substrate. Next, the cured pattern and the electrode pattern were evaluated by the above evaluation method. The results are shown in Table 6. The film thickness of the photosensitive paste layer was in the range of 10 μm ± 1 μm.
[Example 32]
Aluminum powder A1-2 (5 g) shown in Table 1, aluminum alloy powder A2-1 (25 g) and zinc powder A2-20 (10 g) shown in Table 2, glass powder B2 (5 g) shown in Table 3, and Table 4 The photosensitive resin component (1) (55 g) shown was kneaded with a kneader to prepare a photosensitive paste composition (hereinafter also referred to as “photosensitive paste”) in the same manner as in Example 1, except that glass A photosensitive paste layer, a cured pattern, and an electrode pattern were sequentially formed on the substrate. Next, the cured pattern and the electrode pattern were evaluated by the above evaluation method. The results are shown in Table 6. The film thickness of the photosensitive paste layer was in the range of 10 μm ± 1 μm.

TMP: trimethylolpropane (propion oxide modified) triacrylate MTPMP: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propan-1-one DETX: 2,4-diethylthioxanthone MTMS: γ-methacryloxypropyltrimethoxysilane BHHD: 1,7-bis (4-hydroxyphenol) -1,6-heptadiene-3,5-dione MTMS: γ-methacryloxypropyltrimethoxysilane DTNOL: dihydroterpineol

表に示すように、現像後および焼成後のパターン評価では、実施例１、２、４および６〜２３、２５、２５、２６および２８〜３２が特に優れていた。実施例３、５および２７は優れていた。実施例２４は良好であった。焼成後の密着性評価では、実施例１〜３２は良好であった。体積抵抗の評価では、実施例１〜３２は１６〜８０μΩ・ｃｍの範囲に入った。

As shown in the table, Examples 1, 2, 4 and 6 to 23, 25, 25, 26 and 28 to 32 were particularly excellent in pattern evaluation after development and after baking. Examples 3, 5 and 27 were excellent. Example 24 was good. In the adhesion evaluation after firing, Examples 1 to 32 were good. In evaluation of volume resistance, Examples 1-32 entered the range of 16-80 microhm * cm.

[Comparative Examples 1-5]
A photosensitive paste layer, a cured pattern, and an electrode pattern were sequentially formed on a glass substrate in the same manner as in Example 1 except that a photosensitive paste was prepared using the aluminum component, glass powder, and photosensitive resin component shown in Table 5. Formed. Next, the cured pattern and the electrode pattern were evaluated by the above evaluation method. The results are shown in Table 6.

As shown in Table 7, Comparative Examples 1 and 2 were particularly excellent in pattern evaluation after development and after baking. Comparative Example 5 is good. Comparative examples 3 and 4 are defective. In the adhesion evaluation after firing, Comparative Examples 1 to 4 are good. Comparative example 5 is defective. In the evaluation of the volume resistance, Comparative Examples 1 to 4 were in the range of 15 to 500 μΩ · cm.

FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC type plasma display panel. FIG. 2 is a schematic diagram showing a cross-sectional shape of a general field emission display.

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

Claims (6)

(A1) Conductive component (A) containing 30 to 5% by weight of aluminum powder and (A2) 70 to 95% by weight of at least one selected from aluminum alloy powder and zinc powder,
Alkali-soluble resin (C),
A photosensitive paste composition comprising a polyfunctional (meth) acrylate (D) and a photopolymerization initiator (E). The photosensitive paste composition according to claim 1, wherein the aluminum alloy powder contains aluminum and at least one selected from zinc, indium, titanium, bismuth, silicon, copper, lanthanoid, manganese, and magnesium. The photosensitive paste composition according to claim 1, wherein the aluminum content in the aluminum alloy powder is 1 to 60% by weight.   2. The photosensitive paste composition according to claim 1, further comprising a glass powder (B) having a 50% by weight particle size of 0.2 to 4 μm.   The photosensitive paste composition according to claim 2, wherein the glass powder (B) contains a glass powder having a softening point of 350 to 700 ° C. Forming a photosensitive paste layer comprising the photosensitive paste composition according to claim 1 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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