JP2010210864A - Aluminum-containing photosensitive resin composition and method for forming pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inexpensive aluminum-containing photosensitive resin composition, from which a pattern with a low resistance value can be formed, and to provide a method for forming a pattern by using the photosensitive resin composition. <P>SOLUTION: The aluminum-containing photosensitive resin composition contains: (A) aluminum powder; (C) an alkali-soluble resin having 5 to 20 wt.% of structural units derived from (meth)acrylic acids, 25 to 95 wt.% of structural units derived from acrylates, and 0 to 70 wt.% of structural units derived from methacrylates; (D) a polyfunctional (meth)acrylate; and (E) a photopolymerization initiator. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

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

  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, 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, 110 is a protective layer made of, for example, magnesium oxide.

  In a color FPD, a color filter (red / green / blue) or a black matrix may be provided between the glass substrate and the dielectric layer in order to obtain a high contrast image.

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

  Therefore, at present, pattern formation by photolithography is mainly used. For example, when manufacturing an electrode, by using a photosensitive silver paste in the photolithography method, it is possible to form a large and high-definition pattern which is a problem that cannot be dealt with by the screen printing method (for example, Patent Documents 1 and 2).

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

  Therefore, at present, the use of aluminum as a conductive particle to replace expensive silver is being studied. However, since aluminum is more easily oxidized than silver, there is a problem in that the resistance value of the pattern increases in the baking process.

JP 09-306343 A JP 2008-001070 A

  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 an inexpensive aluminum-containing photosensitive resin composition capable of forming a pattern having a low resistance value. Moreover, this invention aims at providing the pattern formation method using the said aluminum containing photosensitive resin composition.

  The present inventors have intensively studied to solve the above problems. As a result, it was found that, when aluminum was used as the conductive particles and an alkali-soluble resin mainly composed of methacrylic acid ester was used as the binder resin, the resistance value of the pattern increased in the firing step. In this regard, in Patent Document 2, an alkali-soluble resin mainly composed of a methacrylic acid ester is preferred as a binder resin (paragraph [0028], Examples, etc.), and no further study of an alkali-soluble resin has been made. .

  The present inventors conducted further studies based on the above findings. As a result, the present inventors have found that the above problems can be solved by using a resin mainly composed of an acrylate ester as an alkali-soluble resin together with the aluminum powder, and have completed the present invention.

That is, the present invention and preferred embodiments thereof relate to the following [1] to [5].
[1] (A) Aluminum powder, (C) 5 to 20% by weight of structural unit derived from (meth) acrylic acid, 25 to 95% by weight of structural unit derived from acrylate ester, and structural unit derived from methacrylic acid ester An aluminum-containing photosensitive resin composition comprising: an alkali-soluble resin having a content of 0 to 70% by weight; (D) a polyfunctional (meth) acrylate; and (E) a photopolymerization initiator.

  [2] The alkali-soluble resin (C) contains 15 to 20% by weight of a structural unit derived from (meth) acrylic acid, 50 to 85% by weight of a structural unit derived from an acrylate ester, and a structural unit derived from a methacrylic acid ester. The aluminum-containing photosensitive resin composition as described in [1] above, which is an alkali-soluble resin having a content of 0 to 35% by weight.

  [3] The glass powder (B) is further contained, and the glass powder (B) has a 50% by weight average particle diameter (D50) of 0.2 to 4.0 μm. [2] The aluminum-containing photosensitive resin composition according to [2].

  [4] The glass powder (B) has a softening point of 350 to 700 ° C. and contains the glass powder (B) in a range of 0.5 to 40% by weight with respect to the entire photosensitive resin composition. The aluminum-containing photosensitive resin composition as described in [3] above.

  [5] (1) A step of forming a photosensitive resin layer comprising the aluminum-containing photosensitive resin composition according to any one of [1] to [4] on a substrate, and (2) an exposure treatment of the resin layer. Forming a latent image of the pattern, (3) a step of developing the resin layer to form a pattern, and (4) a step of baking the pattern.

  According to the present invention, an inexpensive aluminum-containing photosensitive resin composition capable of forming a pattern having a low resistance value is provided. Moreover, according to this invention, the pattern formation method using the said aluminum containing photosensitive resin composition is provided.

  Since the aluminum-containing photosensitive resin composition of the present invention has the above-mentioned properties, it is used as a forming material for display panel members such as FPD, a highly mounted material member for electronic parts, and a solar cell member, particularly an electrode forming material. It can be preferably used.

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

  Hereinafter, the aluminum-containing photosensitive resin composition of the present invention (hereinafter also simply referred to as “photosensitive resin composition”) and the pattern forming method will be described in detail including preferred embodiments. In the following description, a layer before exposure formed using the photosensitive resin composition is referred to as a “photosensitive resin layer”, and a pattern obtained by exposing and developing the resin layer or a pattern after baking is described. Collectively, it is also simply called “pattern”.

[Photosensitive resin composition]
The photosensitive resin composition of this invention contains the aluminum powder (A) demonstrated below, alkali-soluble resin (C), polyfunctional (meth) acrylate (D), and a photoinitiator (E). Moreover, the photosensitive resin composition of this invention may contain glass powder (B) and another additive other than said each component.

<< Aluminum powder (A) >>
Examples of the aluminum powder (A) include at least one metal powder selected from aluminum powder and aluminum alloy powder. Further, the metal powder may be included with a fatty acid. Such metal powder or metal powder clathrated with a fatty acid is suitable for forming an electrode constituting a display panel such as an FPD.

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

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

  The 50% by weight average particle size (D50) of the aluminum powder (A) is preferably 2.0 to 20.0 μm, and more preferably 5.0 to 15.0 μm. When D50 is in the above range, the exposure light in the exposure step can sufficiently reach the bottom of the photosensitive resin layer, and a high-definition pattern can be obtained. In the present invention, the average particle diameter is a value measured by a laser diffraction method, and the same applies to other powders. D50 refers to the particle size of a powder having a particle size distribution, in which the powder is accumulated from those having a small particle size, and the cumulative amount is 50% by weight of the total powder amount.

Further, the shape of the aluminum powder (A) is not particularly limited, but is preferably spherical, flaky or irregular, and more preferably spherical or flaky.
In the photosensitive resin composition of the present invention, the aluminum powder (A) is usually contained in the range of 15 to 70% by weight, preferably 30 to 70% by weight, more preferably 50 to 70% by weight. When content of aluminum powder (A) exists in the said range, the oxidation of aluminum powder (A) can be prevented in a baking process, and a low-resistance and high-definition pattern can be manufactured.

  In addition to the aluminum powder (A), other metal-based powders (for example, Pt, Au, Ag, Cu, Sn, Ni, Fe, Zn, W, Mo, or a compound thereof, as long as the object of the present invention is not impaired. May also be used. For example, the other metal-based powder can be used in an amount of 25 parts by weight or less with respect to 100 parts by weight of the aluminum powder (A).

<< Glass Powder (B) >>
It is preferable that the photosensitive resin composition of this invention contains glass powder (B) from a viewpoint of the pattern adhesiveness after baking. The glass powder (B) can be appropriately selected according to the application of the pattern formed by the photosensitive resin composition of the present invention (FPD member, electronic component advanced mounting material member, etc.).

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). Mixture of bismuth oxide, boron oxide and silicon oxide (Bi ₂ O ₃ —B ₂ O ₃ —SiO ₂ system);
6). A mixture of zinc oxide, phosphorus oxide and silicon oxide (ZnO—P ₂ O ₅ —SiO ₂ system);
7). A mixture of zinc oxide, boron oxide and potassium oxide (ZnO—B ₂ O ₃ —K ₂ O system);
8). Mixture of phosphorus oxide, boron oxide and aluminum oxide (P ₂ O ₅ —B ₂ O ₃ —Al ₂ O ₃ system);
9. A mixture of zinc oxide, phosphorus oxide, silicon oxide, aluminum oxide (ZnO—P ₂ O ₅ —SiO ₂ —Al ₂ O ₃ system);
10. A mixture of zinc oxide, phosphorus oxide and titanium oxide (ZnO—P ₂ O ₅ —TiO ₂ system);
11. A mixture of zinc oxide, boron oxide, silicon oxide and potassium oxide (ZnO—B ₂ O ₃ —SiO ₂ —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);
16. A mixture of boron oxide and silicon oxide (B ₂ O ₃ —SiO ₂ system);
Of these, environment-friendly lead-free glass is particularly preferable.

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

  The softening point of the glass powder (B) is preferably 350 to 700 ° C, and more preferably 400 to 620 ° C. The glass powder having such a softening point is suitable for forming an electrode constituting a display panel such as an FPD. In addition, in this invention, the softening point of glass powder (B) is a value measured on the measurement conditions in the Example mentioned later by DSC measurement.

  When the softening point of the glass powder (B) is lower than the above range, the glass powder may melt at a stage where the organic substance such as the alkali-soluble resin (C) is not completely decomposed and removed in the pattern firing step. For this reason, some organic substances remain in the fired pattern to be formed, and as a result, the resistance value of the pattern tends to increase. On the other hand, when the softening point of the glass powder (B) exceeds the above range, the pattern needs to be fired at a high temperature equal to or higher than the softening point, so that the support such as the glass substrate is likely to be distorted.

  The glass powder (B) is mixed, melted and solidified so as to have a predetermined composition and softening point using a conventionally known method and apparatus, and then pulverized to have a predetermined average particle size. Can be obtained. Moreover, the shape of glass powder (B) is not specifically limited, such as an indefinite shape.

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

  In the photosensitive resin composition of the present invention, the glass powder (B) is preferably in the range of 0.5 to 40% by weight, more preferably 0.5 to 25% by weight, particularly preferably 1.0 to 20% by weight. Included. When the content of the glass powder (B) is in the above range, the resistance value is less affected and a pattern having excellent adhesion after firing can be formed.

<< Alkali-soluble resin (C) >>
In this invention, alkali-soluble resin (C) which has the following structural unit in the following range is used. By using such an alkali-soluble resin (C), it is possible to prevent an increase in the resistance value of the pattern in the baking process even if the resin composition contains aluminum.

  The alkali-soluble resin (C) contains 5 to 20% by weight of a structural unit derived from (meth) acrylic acid, 25 to 95% by weight of a structural unit derived from an acrylate ester, and 0 to 70 structural units derived from a methacrylic acid ester. 10 to 20% by weight of structural units derived from (meth) acrylic acid, 35 to 90% by weight of structural units derived from acrylate ester, and 0 to 55 structural units derived from methacrylic acid ester Preferably, the structural unit is in the range of 15% by weight; the structural unit derived from (meth) acrylic acid is 15 to 20% by weight, the structural unit derived from acrylate ester is 50 to 85% by weight, and the structural unit derived from methacrylic acid ester is 0 It is particularly preferred to have a content in the range of ˜35% by weight. However, the total structural unit of the alkali-soluble resin (C) is 100% by weight.

  Moreover, it is good also considering the ratio of each said structural unit as a preparation ratio of (meth) acrylic acid, acrylic ester, and methacrylic ester with respect to 100 weight% of raw material monomers at the time of synthesize | combining alkali-soluble resin (C).

  In the present invention, “alkali-soluble” refers to a property of being dissolved in an alkali developer to such an extent that the intended development processing is possible. The alkali-soluble resin (C) as described above can be synthesized according to a conventionally known method.

Alkali-soluble resin (C) may be used individually by 1 type, and may use 2 or more types together.
The alkali-soluble resin (C) may have structural units derived from other monomers other than structural units derived from (meth) acrylic acid, acrylic acid esters and methacrylic acid esters, but (meth) acrylic acid, It preferably comprises only structural units derived from acrylic acid esters and methacrylic acid esters.

<(Meth) acrylic acid>
When the content of the structural unit derived from (meth) acrylic acid is in the above range, good alkali solubility can be imparted to the resin. In addition, in this invention, content of the structural unit derived from (meth) acrylic acid is content of these total, when both the structural unit derived from acrylic acid and the structural unit derived from methacrylic acid are contained. .

<Acrylic acid ester, methacrylic acid ester>
When the content of the structural unit derived from the acrylate ester is in the above range, it is possible to impart good plasticity to the resin and to form a low resistance pattern by using such an alkali-soluble resin. Can do.

  In addition, since the content of the structural unit derived from the methacrylic acid ester is in the above range, good combustibility can be imparted to the resin, and by using such an alkali-soluble resin, a low resistance pattern can be obtained. Can be formed.

Hereinafter, although the specific example of the said acrylic acid ester and methacrylic acid ester is shown, these are collectively described only as (meth) acrylic acid ester.
Examples of the (meth) acrylic acid ester include (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, lauryl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Alkyl esters;
Hydroxyl group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate;
Alkoxy group-containing (meth) acrylic acid esters such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate;
Epoxy group-containing (meth) acrylic acid esters such as glycidyl (meth) acrylate;
2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) acryloyloxypropyl hexahydrophthalic acid, 2- (meth) ) Acryloyloxypropyl hydrogen phthalate, 2- (meth) acryloyloxypropyl hexahydrohydrogen phthalate, 2- (meth) acryloyloxypropyl tetrahydrohydrogen phthalate, ω-carboxy-polycaprolactone mono (meth) acrylate, succinic acid mono (2- Carboxyl group-containing (meth) acrylic acid esters such as (meth) acryloyloxyethyl);
Benzyl (meth) acrylate, 2-phenylethyl (meth) acrylate, trityl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate And (meth) acrylic acid esters having a cyclic skeleton such as These (meth) acrylic acid esters may be used alone or in combination of two or more.

<Other structural units>
The alkali-soluble resin (C) is from styrene or the like as long as the content of structural units derived from (meth) acrylic acid, acrylic acid ester and methacrylic acid ester is in the above range and does not impair the object of the present invention. Macromonomer having a polymerizable unsaturated group such as (meth) acryloyl group, allyl group, vinyl group at one chain end of the obtained polymer; maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid Carboxyl group-containing monomers such as cinnamic acid, phenolic hydroxyl group-containing monomers such as o-hydroxystyrene, m-hydroxystyrene and p-hydroxystyrene, and alkali-soluble functional groups such as (α-hydroxymethyl) acrylate It may have a structural unit derived from a monomer having a saturated bond .

<Radical polymerization initiator>
The alkali-soluble resin (C) is obtained by copolymerizing the above monomers, and it is preferable to use a radical polymerization initiator during the copolymerization. As the radical polymerization initiator, a radical polymerization initiator used for polymerization of a vinyl monomer can be used. As radical polymerization initiators, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutylnitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 1 , 1′-azobis (1-cyclohexanecarbonitrile), dimethyl-2,2′-azobisisobutyrate, 4,4′-azobis (4-cyanovaleric acid) and the like; t-butylperoxy Examples thereof include organic peroxides such as peroxyesters such as bivalate, t-butylperoxy 2-ethylhexanoate, cumylperoxy 2-ethylhexanoate. These radical polymerization initiators may be used alone or in combination of two or more.
The usage-amount of the said radical polymerization initiator is about 0.1-10 weight part with respect to 100 weight part of all the monomers (a macromonomer is included) used for the said copolymerization.

<Chain transfer agent>
The alkali-soluble resin (C) is obtained by copolymerizing the above monomers, but a chain transfer agent may be used in the copolymerization. Examples of chain transfer agents include α-methylenestyrene dimer, t-dodecyl mercaptan, pentaerythritol tetrakis (3-mercaptopropionic acid), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryl). And oxy) butane. These chain transfer agents may be used individually by 1 type, and may use 2 or more types together.

  In the present invention, the alkali-soluble resin (C) preferably has an SH group (hereinafter, the resin is also referred to as “SH group-containing resin”). Upon irradiation with light, the SH group-containing resin undergoes an ene-thiol reaction with the polyfunctional (meth) acrylate (D), and the resin itself further polymerizes. For this reason, the SH group-containing resin has higher sensitivity than the resin having no SH group. Furthermore, since the molecular weight of the resin is increased by this polymerization, the pattern shape after development is improved.

The SH group-containing resin is a compound having at least two SH groups in one molecule as a chain transfer agent (eg, pentaerythritol tetrakis (3-mercaptopropionic acid), pentaerythritol tetrakis (3-mercaptobutyrate), 1, It can be synthesized by using 4-bis (3-mercaptobutyryloxy) 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 (including macromonomer) used for the copolymerization.

<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 is below the above range, film roughness after development tends to occur. If Mw exceeds the above range, the solubility of the unexposed portion in the developer may be reduced, and the resolution may be reduced.

  The glass transition temperature (Tg) of the alkali-soluble resin (C) is preferably -40 to 120 ° C, more preferably -20 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. Moreover, when the glass transition temperature exceeds the above range, the adhesion between the photosensitive resin layer and a support such as a glass substrate tends to deteriorate. The glass transition temperature can be appropriately adjusted by changing the copolymerization ratio of the monomers.

  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 is difficult to remove the unexposed portion with an alkali developer, and it becomes difficult to form a high-definition pattern. On the other hand, when the acid value exceeds the above range, the exposed 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 resin composition of the present invention, the alkali-soluble resin (C) is preferably contained in the range of 5 to 90% by weight, more preferably 10 to 75% by weight, and particularly preferably 15 to 50% by weight.

  Moreover, it is preferable that the photosensitive resin composition of this invention consists of 5 to 90 weight% of the photosensitive resin component and 95 to 10 weight% of inorganic particles. Inorganic particles refer to aluminum powder (A), other metal powders, glass powder (B), inorganic pigments, etc .; photosensitive resin component refers to a component obtained by removing the inorganic particles from the photosensitive resin composition. Say.

  The photosensitive resin component includes an alkali-soluble resin (C), a polyfunctional (meth) acrylate (D), and a photopolymerization initiator (E), and may further include other additives described later. .

<< Polyfunctional (meth) acrylate (D) >>
The polyfunctional (meth) acrylate (D) includes 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 di (meth) acrylate, etc. Di (meth) acrylates;
Pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane (propylene oxide modified) tri (meth) acrylate, trimethylolpropane (ethylene oxide modified) tri (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylates having three or more functional groups such as (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and benzyl mercaptan tri (meth) acrylate;
Among the hydrogen atoms bonded to the aromatic ring of the above compound, there may be mentioned monomers in which 1 to 5 are substituted with chlorine atoms or bromine atoms. These polyfunctional (meth) acrylates (D) may be used alone or in combination of two or more.

  In the photosensitive resin composition of the present invention, the polyfunctional (meth) acrylate (D) is preferably 10% by weight or more, more preferably 15 to 15%, based on the photosensitive resin component, from the viewpoint of sensitivity to exposure light. It is included in the range of 60% by weight. When content of polyfunctional (meth) acrylate (D) exceeds the said range, the shape of a baking pattern 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)>
As photopolymerization initiator (E), 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-methylpropiophenone, pt -Butyldichloroacetophenone, 4-azidobenzalacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 2,4- Ethyl thioxanthone, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, methyleneanthrone, dibenzosuberone, 2,6-bis (p -Azidobenzylidene) cyclohexanone, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, Michler's ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane-1- ON, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2′-dimethoxy-1, 2-diphenyl eta -1-one, camphorquinone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl Carbonyl compounds such as propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime;
Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenyl Acylphosphine oxide compounds such as phosphine oxide;
Benzyldimethylketanol, benzylmethoxyethyl acetal, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, tetrabromination Examples include carbon, tribromophenyl sulfone, benzoin peroxide, and a combination of a photoreducing dye such as eosin or methylene blue and a reducing agent such as ascorbic acid or triethanolamine. These photopolymerization initiators may be used alone or in combination of two or more.

  In addition to the photopolymerization initiator (E), a sensitizer may be used to improve the exposure sensitivity of the photosensitive resin layer. Examples of the sensitizer include 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 2,4-diethylthioxanthone, 2,3-bis (4 -Diethylaminobenzal) cyclopentanone, 2,6-bis (4-dimethylaminibenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone, 4,4-bis (Diethylamino) -benzophenone, 4,4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, 2- (p- Dimethylaminophenyl vinyl ) -Isonaphthothiazole, 1,3-bis (4-dimethylaminobenzal) acetone, 1,3-carbonyl-bis (4-diethylaminobenzal) acetone, 3,3-carbonyl-bis (7-diethylaminocoumarin) ), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, Examples thereof include 1-phenyl-5-ethoxycarbonylthiotetrazole. The 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 resin composition of the present invention, the photopolymerization initiator (E) (when the sensitizer is also used, the total of the photopolymerization initiator and the sensitizer) is 100 weights of polyfunctional (meth) acrylate (D). The amount is preferably 1 to 50 parts by weight, more preferably 2 to 40 parts by weight with respect to parts. When content of a photoinitiator (E) exceeds the said range, the shape of a baking pattern may deteriorate.

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

<Ultraviolet absorber>
You may mix | blend a ultraviolet absorber with the photosensitive resin composition of this invention. By blending a compound having a high ultraviolet absorption effect, a pattern with a high aspect ratio, high definition and high resolution can be obtained. As the ultraviolet absorber, an organic dye or an inorganic pigment can be used, and among them, an organic dye or an inorganic pigment having a high UV absorption coefficient in a wavelength range of 350 to 450 nm is preferably used.

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

  In the photosensitive resin composition of the present invention, the ultraviolet absorber is 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). included. If the content of the UV absorber is below the above range, the effect of blending the UV absorber may be reduced, and if it exceeds the above range, the effect of blending the UV absorber is large and exposure light reaches the bottom of the photosensitive resin layer. In some cases, the pattern cannot be formed, the pattern cannot be formed, and the film formation strength cannot be maintained.

<Organic solvent>
The photosensitive resin composition of the present invention may contain an organic solvent in order to adjust the viscosity. Organic solvents include terpineol, dihydroterpineol, dihydroterpinel acetate, limonene, carbeol, carvinyl acetate, citronellol, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl cellosolve , Ethyl cellosolve, butyl cellosolve, methoxypropyl acetate, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, bromobenzene, chlorobenzene, dibromobenzene, dichloro Robenzen, bromobenzoic acid, chlorobenzoic acid. An organic solvent may be used individually by 1 type, and may use 2 or more types together. In the photosensitive resin composition of the present invention, the organic solvent is preferably contained in the range of 5 to 60% by weight, more preferably 10 to 40% by weight.

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

<Antioxidant>
In order to prevent oxidation of the alkali-soluble resin (C) during storage, an antioxidant may be added to the photosensitive resin composition of the present invention. Antioxidants 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. In the photosensitive resin composition of the present invention, the antioxidant is preferably contained in the range of 0.001 to 1% by weight.

<Adhesion aid>
In the photosensitive resin composition of the present invention, an adhesion assistant may be blended 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.

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

  In the photosensitive resin composition of the present invention, the adhesion assistant is preferably in the range 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). Included.

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

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

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

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

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

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

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

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

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

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

<Preparation of photosensitive resin composition>
The photosensitive resin composition of the present invention comprises an aluminum powder (A), an alkali-soluble resin (C), a polyfunctional (meth) acrylate (D) and a photopolymerization initiator (E), and a glass powder (B) that is preferably used. And other additives used as necessary are prepared so as to have a predetermined composition ratio, and then mixed and dispersed homogeneously with a three roll or kneader.

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

[Pattern formation method]
The pattern forming method of the present invention includes (1) a step of forming a photosensitive resin layer comprising the above photosensitive resin composition on a substrate (photosensitive resin layer forming step), and (2) an exposure treatment of the resin layer. A step of forming a latent image of the pattern (exposure step), (3) a step of developing the resin layer to form a pattern (development step), and (4) a step of baking the pattern (baking step). It is characterized by including.

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

  The method for applying the photosensitive resin composition on the substrate is not particularly limited as long as it is a method capable of efficiently forming a coating film having a large film thickness (for example, 20 μm or more) and excellent uniformity. . Examples thereof include a coating method using a knife coater, a coating method using a roll coater, a coating method using a doctor blade, a coating method using a curtain coater, a coating method using a die coater, a coating method using a wire coater, and a screen printing method using a screen printing apparatus.

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

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

(2) Exposure process After forming the photosensitive resin layer on a board | substrate by the said photosensitive resin layer formation process, it exposes using an exposure apparatus. As the exposure is performed by ordinary photolithography, a mask exposure method using an exposure mask can be employed. The exposure pattern of the exposure mask varies depending on the purpose, but is, for example, a stripe or lattice having a width of 10 to 500 μm.

Alternatively, a method of directly drawing with a red or blue visible laser beam, an Ar ion laser, or the like without using an exposure mask may be used.
The surface of the photosensitive resin layer is selectively irradiated (exposed) with exposure light such as ultraviolet rays through an exposure mask to form a pattern latent image on the resin layer. As the exposure apparatus, a parallel light exposure machine, a scattered light exposure machine, a stepper exposure machine, a proximity exposure machine, or the like can be used. In addition, when performing exposure of a large area, after applying a photosensitive resin composition on a substrate such as a glass substrate, exposure is performed while transporting the substrate, so that a large area can be obtained with an exposure machine having a small exposure area. Can be exposed.

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

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

(3) Development Step After the exposure, the photosensitive resin layer is developed to form a pattern using the difference in solubility between the photosensitive portion and the non-photosensitive portion in the developer. Development methods (eg, 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 alkali developer such as an alkaline aqueous solution can be used because the alkali-soluble resin (C) is present in the photosensitive resin layer. Moreover, the organic solvent which can melt | dissolve the organic substance in the photosensitive resin layer can also be used. Water may be added to the organic solvent as long as its dissolving power is not lost.

  The photosensitive resin layer contains inorganic particles such as aluminum powder (A), and the inorganic particles are uniformly dispersed by the alkali-soluble resin (C). Therefore, the alkali-soluble resin (C) is developed. The inorganic particles are also removed simultaneously by dissolving in a liquid and washing.

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

  The alkali concentration of the alkaline aqueous solution is usually 0.01 to 10% by weight, preferably 0.1 to 5% by weight. If the alkali concentration is too low, the soluble part is not removed, and if the alkali concentration is too high, the pattern part may be peeled off and the insoluble part may be corroded. The development temperature during development is preferably 20 to 50 ° C. in terms of process control.

  The alkaline aqueous solution may contain additives such as nonionic surfactants and organic solvents. In addition, after the development process with an alkali developer is performed, a washing process is usually performed.

(4) Firing step The firing atmosphere varies depending on the type of the photosensitive resin composition and the substrate. For example, this step is performed in an atmosphere of air, ozone, nitrogen, hydrogen, or the like. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used.

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

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

  The pattern forming method of the present invention is suitable for manufacturing an FPD electrode, particularly a PDP electrode.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited at all by these Examples. In the examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, unless otherwise specified.
First, a method for measuring and evaluating physical properties will be described.

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

[Measurement method of weight average molecular weight (Mw)]
The weight average molecular weight (Mw) is a value 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.

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

[Measurement method of film thickness after firing]
A panel test piece (10 mm × 10 mm × 1.8 mm) was prepared by cutting the fired panel, and the cut surface of the cured layer formed on the panel was scanned with a scanning electron microscope (“S4200” manufactured by Hitachi, Ltd.). The film thickness after firing of the cured layer was measured.

[Measurement method of electrical resistivity (volume resistivity)]
The volume resistivity (μΩ · cm) of the hardened layer formed on the panel was measured under the conditions of a measurement temperature of 25 ° C. and a measurement humidity of 50% using “Resistivity Processor Model Σ-5” manufactured by NPS.

[Synthesis Example 1]
15 parts of methacrylic acid as a raw material monomer, 40 parts of n-butyl acrylate and 45 parts of 2-methoxyethyl acrylate; 1 part of azobisisobutyronitrile (AIBN) as a radical polymerization initiator; pentaerythritol tetrakis (3- 5 parts of mercaptopropionic acid (manufactured by Sakai Chemical Industry Co., Ltd.) was charged into an autoclave equipped with a stirrer, and stirred in 150 parts of terpineol in a nitrogen atmosphere until uniform.

  Next, polymerization was carried out at 80 ° C. for 4 hours, and further the polymerization reaction was continued at 100 ° C. for 1 hour, followed by cooling to room temperature to obtain an alkali-soluble resin (C1) having SH groups. The polymerization rate of the alkali-soluble resin (C1) was 98%, and the weight-average molecular weight of the alkali-soluble resin (C1) was 21400.

[Synthesis Examples 2 to 8]
In Synthesis Example 1, alkali-soluble resins (C2) to (C5) and alkali-soluble resins (1) to (3) were synthesized in the same manner as in Synthesis Example 1 except that the raw material monomers listed in Table 1 were used.

[Example 1]
103.5 parts of aluminum powder (D50 = 2.0 μm) as aluminum powder (A), boron oxide / silicon oxide glass (B ₂ O ₃ —SiO ₂ system, D50 = 2.0 μm) as glass powder (B), 12 parts of a glass powder having a softening point of 520 ° C., 30 parts of an alkali-soluble resin (C1) synthesized as an alkali-soluble resin (C), and polypropylene glycol diacrylate (n≈7) as a polyfunctional (meth) acrylate (D) ) (Trade name M225, manufactured by Toa Gosei Co., Ltd.) 10 parts, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane-1- as photopolymerization initiator (E) 2 parts of ON and 0.5 part of 2,4-diethylthioxanthone as a sensitizer are kneaded with a kneader to give a paste-like composition (hereinafter also referred to as “photosensitive paste”). It was manufactured.

  The photosensitive paste is printed on a panel made of a glass substrate (150 mm × 150 mm × 1.8 mm) to a size of 100 mm square, held at 100 ° C. for 20 minutes and dried to obtain a photosensitive film having a thickness of 10 μm. A functional resin layer was formed.

Next, the photosensitive resin layer was exposed to ultraviolet rays from the upper surface with an ultrahigh pressure mercury lamp having an output of 25 mW / cm ² . The exposure amount was 1000 mJ / cm ² . The photosensitive resin layer after ultraviolet irradiation was baked at 580 ° C. for 30 minutes to obtain a cured layer. About this hardening layer, the film thickness and volume resistivity after baking were measured. The results are shown in Table 2.

[Examples 2 to 5, Comparative Examples 1 to 3]
In Example 1, the cured layer was obtained like Example 1 except having prepared the photosensitive paste using alkali-soluble resin of Table 2 as alkali-soluble resin (C). About this hardening layer, the film thickness and volume resistivity after baking were measured. The results are shown in Table 2.

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 (5)

(A) aluminum powder,
(C) 5 to 20% by weight of a structural unit derived from (meth) acrylic acid,
25 to 95% by weight of structural units derived from acrylic acid ester, and 0 to 70% by weight of structural units derived from methacrylic acid ester
An alkali-soluble resin having a range of
An aluminum-containing photosensitive resin composition comprising (D) a polyfunctional (meth) acrylate, and (E) a photopolymerization initiator. The alkali-soluble resin (C) is
15 to 20% by weight of a structural unit derived from (meth) acrylic acid,
A structural unit derived from an acrylate ester is 50 to 85% by weight, and a structural unit derived from a methacrylic acid ester is 0 to 35% by weight.
The aluminum-containing photosensitive resin composition according to claim 1, which is an alkali-soluble resin having a range of (B) further containing glass powder,
The aluminum-containing photosensitive resin composition according to claim 1 or 2, wherein the glass powder (B) has a 50 wt% average particle size (D50) of 0.2 to 4.0 µm.   The softening point of the glass powder (B) is 350 to 700 ° C., and the glass powder (B) is contained in the range of 0.5 to 40% by weight with respect to the entire photosensitive resin composition. The aluminum-containing photosensitive resin composition according to claim 3. (1) The process of forming the photosensitive resin layer which consists of an aluminum containing photosensitive resin composition in any one of Claims 1-4 on a board | substrate,
(2) a step of exposing the resin layer to form a latent image of a pattern;
(3) A step of developing the resin layer to form a pattern; and (4) A step of baking the pattern.

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