KR101106921B1 - Photosensitive paste composition and pattern forming method - Google Patents

Abstract

An object of the present invention is to provide a photosensitive paste composition which is inexpensive, can form a high precision fine pattern, and has a thin film and high adhesive strength for ceramic, silicon and glass substrates.

The present invention contains an aluminum powder (A), alkali-soluble resin (C), polyfunctional (meth) acrylate (D), and a photopolymerization initiator (E) having a 50 wt% particle size (D50) of 2.0 to 20.0 µm. The present invention relates to a photosensitive paste composition.

Photosensitive paste composition, aluminum powder, alkali-soluble resin, polyfunctional (meth) acrylate, photoinitiator, glass powder

Description

Photosensitive paste composition and pattern formation method {PHOTOSENSITIVE PASTE COMPOSITION AND PATTERN FORMING METHOD}

The present invention relates to a photosensitive paste composition and a pattern forming method. More specifically, in the production of circuit boards having electrodes used for display panels such as flat panel displays, high-mount materials for electronic components, solar cell materials, and the like, it can be preferably used for forming highly sensitive and high-precision patterns. It relates to a photosensitive paste composition and a pattern forming method using the composition.

In recent years, the demand for high-density and high-precision refinement is increasing about the pattern processing in a circuit board and a display panel. Among the display panels that are increasing in demand, flat panel displays (hereinafter, also referred to as "FPD") such as plasma display panels (hereinafter referred to as "PDP") and field emission displays (hereinafter referred to as "FED") are especially noteworthy. I am getting it.

1 is a schematic diagram showing a cross-sectional shape of an AC PDP. In FIG. 1, 101 and 102 are opposed glass substrates, 103 and 111 are partition walls, and cells are partitioned by the glass substrate 101, the glass substrate 102, the rear partition 103, and the front partition 111. It is. 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 lowering the resistance of the transparent electrode 104, 106 is fixed to the glass substrate 102 It is an address electrode. 107 is a fluorescent material retained in the cell, 108 is a dielectric layer formed on the surface of the glass substrate 101 to cover the transparent electrode 104 and the bus electrode 105, and 109 is a glass substrate to cover the address electrode 106. It is a dielectric layer formed on the surface of 102, and 110 is a protective layer containing magnesium oxide, for example.

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

In recent years, larger size and high precision refinement are progressing in FPD, and accordingly, the improvement of the pattern processing technique is desired. However, there is a problem that the demand for pattern precision due to the enlargement of the panel and the refinement of the high precision becomes very strict, and that the screen printing method, which is a conventional method, cannot cope. Therefore, pattern formation by the photolithography method is used.

In the production of the electrode by the photolithography method, by using the photosensitive silver paste method, it becomes possible to form large and high-precision fine patterns, a problem which cannot be coped with by the screen printing method.

However, silver is expensive because it is a noble metal, and photosensitive silver paste is also composed of expensive conductive paste. Moreover, as a defect of the photosensitive silver paste, it is easy to produce migration in a high temperature and high humidity environment, and the property that sulfidation generate | occur | produces on the silver surface is mentioned.

In addition, from the recent demand for cost, there is a demand for a material capable of high-precision fine pattern processing while being a cheap inorganic particle-containing photosensitive resin material.

The present invention is intended to solve the problems associated with the prior art as described above, and is inexpensive, can form a high precision pattern, and is a thin film and high adhesive strength for ceramic, silicon and glass substrates. The purpose is to provide. Moreover, an object of this invention is to provide the pattern formation method using the said photosensitive paste composition.

MEANS TO SOLVE THE PROBLEM The present inventors came to complete this invention, as a result of earnestly examining in order to solve the said subject. That is, this invention relates to the following [1]-[4].

[1] What contains an aluminum powder (A), alkali-soluble resin (C), polyfunctional (meth) acrylate (D), and photopolymerization initiator (E) having a 50 wt% particle size (D50) of 2.0 to 20.0 μm The photosensitive paste composition characterized by the above-mentioned.

[2] The photosensitive paste composition according to the above [1], further comprising a glass powder (B) having a 50 wt% particle size (D50) of 0.2 to 4.0 µm.

[3] The photosensitive paste according to the above [2], wherein the glass powder (B) contains a glass powder having a softening point of 350 to 700 ° C. in a proportion of 0.5 to 15% by weight based on the entire photosensitive paste composition. Composition.

[4] A step of forming a photosensitive paste layer comprising the photosensitive paste composition according to any one of the above [1] to [3] on a substrate, a step of exposing the paste layer to form a latent image of a pattern, and the paste. Developing a layer to form a pattern, and firing the pattern.

The photosensitive paste composition of the present invention can form an inexpensive and high precision fine pattern, and can be suitably used for the formation of the members constituting the wiring of the FPD, the formation of the member of the high-mounting material of the electronic component, and the formation of the member of the solar cell. have.

EMBODIMENT OF THE INVENTION Hereinafter, the photosensitive paste composition and pattern formation method of this invention are demonstrated in detail. In addition, below, the layer before exposure formed using the said photosensitive paste composition is also called "photosensitive paste layer."

[Photosensitive Paste Composition]

The photosensitive paste composition of this invention contains the aluminum powder (A), alkali-soluble resin (C), polyfunctional (meth) acrylate (D), and photoinitiator (E) which are demonstrated below. Moreover, glass powder (B) and other additives can also be mix | blended with the said photosensitive paste composition.

<Aluminum Powder (A)>

The aluminum powder (A) used in the present invention has a 50 wt% particle size (D50) of 2.0 to 20.0 µm. Moreover, it is preferable that 50 weight% particle diameter is 5.0-15.0 micrometers. When 50 weight% particle diameter of an aluminum powder (A) exists in the said range, the light at the time of ultraviolet irradiation reaches to the bottom part of a coating film sufficiently, and a high precision fine pattern can be obtained.

As an aluminum powder (A), when forming the "electrode" which comprises FPD, for example, 1 or more types of metal powder selected from an aluminum powder and its compound are mentioned. More preferably, at least 1 type of metal powder selected from the aluminum powder in which fatty acid is contained and its compound is mentioned. In addition, the shape of the aluminum powder (A) is not particularly limited. For example, a spherical shape or a flake shape can be used.

As said fatty acid, For example, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelagonic acid, lauric acid, myristic acid, pentadecyl acid, palmitic acid, palmitoyl acid, margaric acid, Stearic acid, oleic acid, basenic acid, linoleic acid, linolenic acid, nonadecanoic acid, arachidic acid, arachidonic acid, behenic acid, lignocelenic acid, nerbonic acid, serotic acid, montanic acid, melisic acid and the like.

In this invention, content of aluminum powder (A) is 15-70 weight% normally with respect to the whole photosensitive paste composition, Preferably it is 30-70 weight%, More preferably, it is 35-65 weight%. If content of an aluminum powder (A) exists in the said range, it is excellent in electroconductivity.

In addition, in this invention, an aluminum powder (A) contains another metal (for example, Pt, Au, Ag, Cu, Sn, Ni, Fe, Zn, W, Mo, and these compounds) within 20 weight%. You may.

<Glass Powder (B)>

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

Here, as a glass powder contained in the said composition for forming the "electrode" which comprises FPD, a softening point becomes like this. Preferably, the glass powder exists in the range of 350-700 degreeC, More preferably, 400-620 degreeC. . In the case where the softening point of the glass powder is less than 350 ° C., the electrode is formed because the glass powder is melted in a step in which an organic substance such as a binder resin is not completely decomposed and removed in a baking step of a pattern obtained by exposing and developing the photosensitive paste layer. A part of organic substance may remain in the inside. As a result, the said electrode is colored and its light transmittance tends to fall. On the other hand, when the softening point of glass powder exceeds 700 degreeC, since baking needs to be carried out at higher temperature than 700 degreeC, deformation | transformation etc. are easy to generate | occur | produce in a glass substrate.

As a specific example of preferable glass powder (B),

1. a mixture of lead oxide, boron oxide, and silicon oxide (PbO-B ₂ O ₃ -SiO _{2 type} ),

2. a mixture of zinc oxide, boron oxide, and silicon oxide (ZnO-B ₂ O ₃ -SiO _{2 type} ),

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, and silicon oxide (PbO-ZnO-B ₂ O ₃ -SiO _{2 type} ),

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 type} ),

7. a mixture of zinc oxide, boron oxide, potassium oxide (ZnO-B ₂ O ₃ -K ₂ O system),

8. a mixture of phosphorus oxide, boron oxide 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, potassium oxide (ZnO-B ₂ O ₃ -SiO ₂ -K ₂ O type),

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, aluminum oxide (B ₂ O ₃ -SiO ₂ -Al ₂ O ₃ system),

15. A mixture of boron oxide, silicon oxide, sodium oxide (B ₂ O ₃ -SiO ₂ -Na ₂ O system), and the like. Among these, the lead-free glass which considered the environment especially is preferable.

Content of a glass powder (B) is 0.5-35 weight% normally with respect to the whole photosensitive paste composition, for example when forming an electrode member. Preferably it is 0.5-25 weight%. More preferably, it is 1.0-20 weight%. It is especially preferable to contain the glass powder whose softening point is 350-700 degreeC in the ratio of 0.5-15 weight% with respect to the whole photosensitive paste composition, and it is more preferable to contain it in the ratio of 1.0-10 weight%.

In addition, although the average particle diameter of glass powder (B) is suitably selected in consideration of the shape of the pattern to manufacture, it is preferable that 50 weight% particle size (D50) of glass powder (B) is 0.2-4.0 micrometer. Moreover, it is more preferable that 50 weight% particle diameter (D50) is 0.5-3.8 micrometers. Moreover, it is preferable that 10 weight% particle size (D10) is 0.05-0.5 micrometer, and 90 weight% particle size (D90) is 10-20 micrometer. When the average particle diameter of a glass powder (B) exists in the said range, the light at the time of ultraviolet irradiation reaches to the bottom part of a coating film sufficiently, and a high precision fine pattern can be obtained.

<Alkali-soluble resin (C)>

The alkali-soluble resin (C) used in the present invention is not particularly limited as long as it is alkali-soluble. In addition, in this invention, "alkali solubility" means the property melt | dissolved in an alkaline developing solution to the extent that the target image development process is possible.

As alkali-soluble resin (C), the copolymer of the following alkali-soluble functional group containing monomer (C1) and (meth) acrylic-acid derivative (C2) is preferable.

`` Alkali-soluble functional group-containing monomer (C1) ''

As the alkali-soluble functional group-containing monomer (C1), (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, succinic acid mono (2- (meth) acryloyloxyethyl) , 2-methacryloyloxyethyl phthalate, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropylhydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2-acrylo Carboxyl group-containing monomers such as yloxypropyltetrahydrohydrophthalphthalate 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;

The monomer which has alkali-soluble functional groups and unsaturated bonds, such as phenolic hydroxyl group containing monomers, such as o-hydroxy styrene, m-hydroxy styrene, and p-hydroxy styrene, is mentioned.

Among these monomers, (meth) acrylic acid, 2-methacryloyloxyethyl phthalic acid, 2-acryloyloxyethylhydrogen phthalate, 2-acryloyloxypropylhydrogen phthalate, 2-acryloyloxypropyl hexahydro Hydrogenphthalate, 2-acryloyloxypropyltetrahydrohydrogenphthalate, and 2-hydroxyethyl (meth) acrylic acid are preferable.

By copolymerizing an alkali-soluble functional group containing monomer (C1), alkali solubility can be provided to resin. Content of the structural unit derived from this alkali-soluble functional group containing monomer (C1) is 5 to 90 weight% normally in all the structural units of alkali-soluble resin (C), Preferably it is 10 to 80 weight%, Especially preferably, Is 15 to 70% by weight.

`` (Meth) acrylic acid derivative (C2) ''

The (meth) acrylic acid derivative (C2) is not particularly limited as long as it is a (meth) acrylic acid derivative copolymerizable with an alkali-soluble functional group-containing monomer (C1). For example, methyl (meth) acrylate, ethyl (meth) acrylate, n -Butyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-ethylhexyl ( Meth) acrylate, phenoxyethyl (meth) acrylate, trityl (meth) acrylate, cyclohexyl (meth) acrylate, isoboroyl (meth) acrylate, glycidyl (meth) acrylate, dish (Meth) acrylates other than the said monomer (C1), such as clofentanyl (meth) acrylate, etc. are mentioned.

In the present invention, instead of the (meth) acrylic acid derivative (C2) or in addition to the (meth) acrylic acid derivative (C2), for example, styrene, methyl (meth) acrylate, ethyl (meth) acrylate, benzyl ( The macromonomer etc. which have polymerizable unsaturated groups, such as a (meth) acryloyl group, an allyl group, and a vinyl group, can also be used for one chain end of the polymer obtained from a meth) acrylate.

<< radical polymerization initiator >>

At the time of the said copolymerization, it is preferable to use a radical polymerization initiator. As a radical polymerization initiator, the radical polymerization initiator used for superposition | polymerization of a vinyl monomer can be used. For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis (2-methylbutyl nitrile), 2,2'- azobis (2, 4- dimethylvaleronitrile), 1 Azo compounds such as 1'-azobis (1-cyclohexanecarbonitrile), dimethyl-2,2'-azobisisobutyrate, and 4,4'-azobis (4-cyanovaleric acid); Organic peroxides, such as peroxy esters, such as t-butyl peroxy pivalate, t-butyl peroxy 2-ethylhexanoate, and cumyl peroxy 2-ethylhexanoate, etc. are mentioned. These radical polymerization initiators may be used individually by 1 type, and may use 2 or more types together. The usage-amount of these radical polymerization initiators is about 0.1-10 weight part with respect to 100 weight part of all monomers used for the said copolymerization.

≪Chain Transfer Agent≫

A chain transfer agent can also be used at the time of the said copolymerization. Examples of the chain transfer agent include α-methylene styrene dimer, t-dodecyl mercaptan, pentaerythritol tetrakis (3-mercaptopropionic acid), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4- Bis (3-mer capto butyryloxy) butane etc. are mentioned.

The usage-amount of the said chain transfer agent is about 0.1-10 weight part normally with respect to 100 weight part of all monomers used for the said copolymerization.

The weight average molecular weight (also called "Mw") of alkali-soluble resin (C) is polystyrene conversion value measured by the gel permeation chromatography (GPC), Preferably it is 5000-100000, More preferably, it is 10000-80000. . Mw can be controlled by appropriately selecting conditions such as a copolymerization ratio of the monomer, a chain transfer agent, and a polymerization temperature. When Mw is lower than the said range, film | membrane roughness after image development will become easy to occur, and when Mw exceeds the said range, the solubility to the developing solution of an unexposed part may fall and the resolution may fall.

The glass transition temperature (Tg) of alkali-soluble resin (C) becomes like this. Preferably it is 0-120 degreeC, More preferably, it is 10-100 degreeC. When the glass transition temperature is lower than the above range, it is easy to generate a tag in the coating film and tends to be difficult to handle. Moreover, when glass transition temperature exceeds the said range, adhesiveness of the photosensitive paste layer and the glass substrate which is a support body worsens, and when using the transfer film mentioned later, the said paste layer may not be able to be transferred. In addition, glass transition temperature can be suitably adjusted by changing the quantity of alkali-soluble functional group containing monomer (C1) and (meth) acrylic-acid derivative (C2).

The acid value of alkali-soluble resin (C) becomes like this. Preferably it is 20-200 mgKOH / g, More preferably, it is 30-160 mgKOH / g. If the acid value is less than 20 mgKOH / g, the unexposed portion after the exposure is difficult to be quickly removed by the alkaline developer, and there is a tendency that high-precision fine pattern formation becomes difficult. Moreover, when the acid value exceeds 200 mgKOH / g, the part hardened by exposure light also becomes easy to erode by alkaline developing solution, and it exists in the tendency which high precision fine pattern formation becomes difficult.

In the photosensitive paste composition of this invention, the photosensitive resin component means the part except the inorganic particle from the said composition, ie, the whole organic component which has a photosensitive function. Here, the said inorganic particle refers to aluminum powder (A), glass powder (B), etc.

Alkali-soluble resin (C), polyfunctional (meth) acrylate (D), a photoinitiator (E) are contained in the said photosensitive resin component, Furthermore, a sensitizer, a sensitizer, an organic ultraviolet absorber, a polymerization inhibitor, and oxidation Additive components, such as an inhibitor, a plasticizer, a thickener, an organic solvent, an adhesion | attachment adjuvant, a dissolution promoter, a dispersing agent, an antisettling agent of each component, a leveling agent, can be added.

It is preferable that the photosensitive paste composition of this invention contains 5 to 90 weight% of the photosensitive resin component and 95 to 10 weight% of inorganic particle.

<Multifunctional (meth) acrylate (D)>

The photosensitive paste composition of this invention contains a photosensitive component. As said photosensitive component, there exist generally a photoinsoluble type and a photo-solubilization type.

As a photoinsoluble type, (i) a photosensitive monomer or oligomer containing at least one unsaturated group or the like in a molecule thereof, and (ii) a photosensitive compound such as an aromatic diazo compound, an aromatic azide compound or an organic halogen compound And (iii) so-called diazo resins such as condensates of diazo amines and formaldehydes.

As photo-solubilizable, (iv) complexes of inorganic or organic acids of diazo compounds, containing quinone diazos, (v) quinone diazos combined with a suitable polymeric binder, e.g. naphthoquinones of phenol resins -1,2-diazide-5-sulfonic acid ester, and the like.

In the present invention, all of the above-mentioned materials can be used, but since it can be conveniently used by mixing with the said inorganic particle, the polyfunctional (meth) acrylate classified into said (i) is used as an essential component.

Specific examples of the polyfunctional (meth) acrylate (D) used in the present invention include allylated cyclohexyldi (meth) acrylate, 2,5-hexanedi (meth) acrylate, and 1,4-butanedioldi ( 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 cyclohexyldi (meth) acrylate, neopentyl glycoldi (meth) acrylate, propylene glycoldi (meth) acrylate, polypropylene glycol di ( Di (meth) acrylates such as meth) acrylate and triglycerol di (meth) acrylate;

Pentaerythritol tri (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylolpropane PO modified tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, dipentaerythritol hexa (meth 3) such as acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, and benzyl mercaptan (meth) acrylate Functional or more (meth) acrylates;

The monomer etc. which substituted 1-5 with the chlorine or bromine atom among the hydrogen atoms of the aromatic ring in the said compound are mentioned. These polyfunctional (meth) acrylates (D) may be used individually by 1 type, or may be used in combination of 2 or more type.

In the photosensitive paste composition of the present invention, in terms of sensitivity to light, the polyfunctional (meth) acrylate (D) is preferably 10% by weight or more, more preferably 15 to 15, based on the entire photosensitive resin component. It is used in the quantity used as 60 weight%. When content of a polyfunctional (meth) acrylate (D) exceeds the said range, the shape of the member for display panels after baking may deteriorate.

In addition, in the range which does not impair the objective of this invention, with polyfunctional (meth) acrylate (D), styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, chlorinated styrene, styrene bromide, (alpha) -Methylstyrene, chlorinated α-methylstyrene, brominated α-methylstyrene, chloromethylstyrene, hydroxymethylstyrene, carboxymethylstyrene, vinylnaphthalene, vinylanthracene, vinylcarbazole, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone, etc. can also be used.

<Photoinitiator (E)>

As a photoinitiator (E) used by this invention, a benzophenone, methyl o-benzyl benzoate, 4, 4-bis (dimethylamine) benzophenone, 4, 4-bis (diethylamino) benzophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenylketone, dibenzylketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylaceto Phenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, thioxanthone, 2-methyl thioxanthone, 2-chloro thioxanthone, 2-isopropyl thioxanthone, 4-iso Propyl thioxanthone, 1-chloro-4-propyl thioxanthone, 2,4-diethyl thioxanthone, benzyldimethyl ketanol, benzylmethoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, Anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberon, methyleneanthrone, 4-azidebenzalacetophenone , 2,6-bis (p-azidebenzylidene) cyclohexanone, 2,6-bis (p-azidebenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadione- 2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycar Bonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, Michler's ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholine No-1-propane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 2-hydroxy-2-methyl-1-phenyl-propane-1 -One, 2,2'-dimethoxy-1,2-diphenylethan-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphineoxide, 2,4 , 6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphineoxide, naphthalenesulfonylchloride, quinoline sulfonylchloride, N-phenylthioacridone, 4,4 -Azobisisobutyronitrile, diphenyl disulfide And photoreducing pigments such as benzthiazol disulfide, triphenylhorphine, camphorquinone, carbon tetrabromide, tribromophenylsulfone, benzoin peroxide and eosin and methylene blue, and reducing agents such as ascorbic acid and triethanolamine; And combinations thereof. A photoinitiator (E) may be used individually by 1 type, or may be used in combination of 2 or more type.

Content of a photoinitiator (E) becomes like this. Preferably it is 1-50 weight part, More preferably, it is 2-40 weight part with respect to 100 weight part of polyfunctional (meth) acrylates (D). When content of a photoinitiator (E) exceeds the said range, the shape of the member for display panels after baking may deteriorate.

<Ultraviolet absorber>

In this invention, it is also effective to add a ultraviolet absorber in the photosensitive paste composition. By adding a compound with a high ultraviolet absorption effect, a high aspect ratio, high precision fine, and a high resolution pattern are obtained. As the ultraviolet absorber, an organic dye or an inorganic pigment can be used, and among these, an organic dye or an inorganic pigment having a high UV absorption coefficient in the wavelength range of 350 to 450 nm is preferably used.

Specifically, azo dyes, amino ketone dyes, xanthene dyes, quinoline dyes, amino ketone dyes, anthraquinone dyes, benzophenone dyes, diphenylcyanoacrylate dyes, triazine dyes, p Organic dyes such as aminobenzoic acid dyes; Inorganic pigments, such as zinc oxide, titanium oxide, and cerium oxide, can be used. Among these, for example, when the insulating film is formed using the photosensitive paste composition of the present invention, since organic dyes do not remain in the insulating film after firing, since the deterioration of the insulating film properties can be reduced, the reliability of the FPD is preferable. In view of the above, inorganic pigments such as zinc oxide, titanium oxide and cerium oxide are more preferable.

The inorganic pigment may be added in an amount of preferably 0.001 to 5 parts by weight, more preferably 0.01 to 1 part by weight based on 100 parts by weight of the glass powder (B). If the amount is less than 0.001 part by weight, the effect of adding the ultraviolet absorber is decreased. If the amount is more than 5 parts by weight, the effect of the ultraviolet absorber is so great that light does not reach the lower part of the film. There is.

<Sensitizer>

A sensitizer can also be added to the photosensitive paste composition of this invention in order to improve exposure sensitivity. As a sensitizer, 2-methyl thioxanthone, 2-chloro thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 1-chloro-4- propyl thioxanthone, 2, 4-diethyl thioxanthone, 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 ) Calcon, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) -isonnaphthothiazole, 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-tolyl diethanolamine, N-phenylethanolamine, dimethylamino This premature birth and the like can be mentioned isoamyl, diethylamino benzoic acid isoamyl, 3-phenyl-5-benzoyl-thio-tetrazole, 1-phenyl-5-ethoxycarbonyl-thio-tetrazole.

The said sensitizer may be used individually by 1 type, or may be used in combination of 2 or more type. In addition, some sensitizers can be used also as a photoinitiator. The sensitizer can be added to the inorganic particles in an amount of preferably 0.01 to 5% by weight, more preferably 0.05 to 3% by weight. If the amount of the sensitizer is too small, the effect of improving the light sensitivity may not be exhibited. If the amount of the sensitizer is too large, the residual ratio of the exposed portion may be too small.

<Polymerization inhibitor>

In order to improve the thermal stability at the time of storage, you may add a polymerization inhibitor to the photosensitive paste composition of this invention. As the polymerization inhibitor, for example, hydroquinone, monoester of hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-t-butyl- p-methylphenol, chloranyl, pyrogallol and the like. The polymerization inhibitor can be added to the photosensitive paste composition in an amount preferably in the range of 0.001 to 1% by weight.

Antioxidant

In order to prevent the oxidation of alkali-soluble resin (C) at the time of storage, you may add antioxidant to the photosensitive paste composition of this invention. As antioxidant, a 2, 6- di-t- butyl- p-cresol, a butylated hydroxyanisole, 2, 6- di-t- 4-ethylphenol, 2, 2-methylene-bis- ( 4-methyl-6-t-butylphenol), 2,2-methylene-bis- (4-ethyl-6-t-butylphenol), 4,4-bis- (3-methyl-6-t-butylphenol ), 1,1,3-tris- (2-methyl-6-t-butylphenol), 1,1,3-tris- (2-methyl-4-hydroxy-t-butylphenyl) butane, bis [ 3,3-bis- (4-hydroxy-3-t-butylphenyl) butyric acid] glycol ester, dilauryl thiodipropionate, triphenyl phosphite, etc. are mentioned. The antioxidant can be added to the photosensitive paste composition in an amount preferably in the range of 0.001 to 1% by weight.

<Organic solvent>

In order to adjust the viscosity of a solution, you may add an organic solvent to the photosensitive paste composition of this invention. Examples of the organic solvent include terpineol, dihydroterpineol, dihydrotapinenyl acetate, limonene, carveol, carvinylacetate, citronellol, diethylene glycol monoethyl ether acetate, and 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, cyclo Pentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid and the like. have. The said organic solvent may be used individually by 1 type, or may mix and use 2 or more types.

<Adhesion aid>

In order to improve the adhesiveness of the photosensitive paste layer and a support body, you may add an adhesion | attachment adjuvant to the photosensitive paste composition of this invention. As the adhesion aid, a silane compound is preferably used. Specific examples of the silane compound include n-propyldimethylmethoxysilane, n-butyldimethylmethoxysilane, n-decyldimethylmethoxysilane, n-hexadecyldimethylmethoxysilane, n-icosane dimethylmethoxysilane, n-propyl Diethyl methoxysilane, n-butyldiethyl methoxysilane, n-decyldiethylmethoxysilane, n-hexadecyldiethylmethoxysilane, n- icosane diethylmethoxysilane, n-butyldipropylmethoxy Silane, n-decyldipropylmethoxysilane, n-hexadecyldipropylmethoxysilane, n-icosane dipropylmethoxysilane, n-propyldimethylethoxysilane, n-butyldimethylethoxysilane, n-decyldimethyl Ethoxysilane, n-hexadecyldimethylethoxysilane, n-diacid diethylethoxysilane, n-propyldiethylethoxysilane, n-butyldiethylethoxysilane, n-decyldiethylethoxysilane, n Hexadecyldiethylethoxysilane, n-diethyl ethoxysilane, n-butyldipropylethoxysilane, n-decyldipropylethoxysilane, n Hexadecyldipropylethoxysilane, n-icosane dipropylethoxysilane, n-propyldimethylpropoxysilane, n-butyldimethylpropoxysilane, n-decyldimethylpropoxysilane, n-hexadecyldimethylpropoxysilane , n-dimethyl dipropoxysilane, n-propyldiethylpropoxysilane, n-butyldiethylpropoxysilane, n-decyldiethylpropoxysilane, n-hexadecyldiethylpropoxysilane, n-ico Acid diethyl propoxysilane, n-butyldipropyl propoxysilane, n-decyldipropyl propoxysilane, n-hexadecyldipropyl propoxysilane, n-icosane dipropyl propoxysilane, n-propylmethyldimethoxysilane , n-butylmethyldimethoxysilane, n-decylmethyldimethoxysilane, n-hexadecylmethyldimethoxysilane, n-icosane methyldimethoxysilane, n-propylethyldimethoxysilane, n-butylethyldimethoxysilane , n-decylethyldimethoxysilane, n-hexadecylethyldimethoxysilane, n-ethyl diethyl ethane Cysilane, n-butylpropyldimethoxysilane, n-decylpropyldimethoxysilane, n-hexadecylpropyldimethoxysilane, n-icosanepropyldimethoxysilane, n-propylmethyldiethoxysilane, n-butylmethyldiethoxy Silane, n-decylmethyldiethoxysilane, n-hexadecylmethyldiethoxysilane, n-diethyl acid diethoxysilane, n-propylethyl diethoxysilane, n-butylethyl diethoxysilane, n-decylethyl diethoxy Cysilane, n-hexadecylethyl diethoxysilane, n-diethyl ethyl diethoxysilane, n-butylpropyl diethoxysilane, n-decylpropyl diethoxysilane, n-hexadecylpropyl diethoxysilane, n- isopropyl acid Diethoxysilane, n-propylmethyldipropoxysilane, n-butylmethyldipropoxysilane, n-decylmethyldipropoxysilane, n-hexadecylmethyldipropoxysilane, n-icosane methyldipropoxysilane , n-propylethyldipropoxysilane, n-butylethyldipropoxysilane, n-decylethyldipropoxysilane , n-hexadecylethyldipropoxysilane, n-hexaethyl dipropoxysilane, n-butylpropyldipropoxysilane, n-decylpropyldipropoxysilane, n-hexadecylpropyldipropoxysilane, n -Icosanepropyldipropoxysilane, n-propyltrimethoxysilane, n-butyltrimethoxysilane, n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-isoacid trimethoxysilane , n-propyltriethoxysilane, n-butyltriethoxysilane, n-decyltriethoxysilane, n-hexadecyltriethoxysilane, n-icosane triethoxysilane, n-propyltripropoxysilane , n-butyltripropoxysilane, n-decyltripropoxysilane, n-hexadecyltripropoxysilane, n-icosane tripropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N- ( 2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysil , 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 may be used individually by 1 type or in combination of 2 or more types.

Content of the said adhesion | attachment adjuvant in the photosensitive paste composition becomes like this. Preferably it is 0.05-15 weight part, More preferably, it is 0.1-10 weight part with respect to 100 weight part of alkali-soluble resin (C).

Dissolution accelerator

It is preferable that the photosensitive paste composition of this invention contains a dissolution promoter for the purpose of expressing sufficient solubility to the developing solution mentioned later. As a dissolution promoter, surfactant is used preferably. Examples of such surfactants include fluorine-based surfactants, silicon-based surfactants, nonionic surfactants, fatty acids, and the like.

As said fluorine-type surfactant, "BM-1000" by the BM CHIMIE company, "BM-1100", "Megapack F142D" by Dainippon Ink & Chemicals Co., Ltd., "Megapack F142D", "Copper F172", "Copper F173" , "F18," Sumitomo 3M Co., Ltd. "Fluorard FC-135", "East FC-170C", "East FC-430", "East FC-431", Asahi Glass Co., Ltd. Manufacture "Suplon S-112", "the copper S-113", "the copper S-131", "the copper S-141", "the copper S-145", "the copper S-382", "the copper SC-101" And commercially available products such as "SC-102", "SC-103", "SC-104", "SC-105", and "SC-106".

As said silicon type surfactant, For example, Toray Dow Corning Silicone Co., Ltd. "SH-28PA", "SH-190", "SH-193", "SZ-6032", "SF-8428" , "DC-57", "DC-190", Shin-Etsu Chemical Co., Ltd. "KP341", Shin-Akita Kasei Co., Ltd. "F-top EF301", "EF303", "EF352" And commercially available products.

As said nonionic surfactant, For example, polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene distylated phenyl ether, polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; Polyoxyethylene dialkyl ester, such as polyoxyethylene dilaurate and polyoxyethylene distearate, etc. are mentioned.

As a commercial item of the said nonionic surfactant, Kao Corporation make "emulsion A-60", "A-90", "A-550", "B-66", "PP-99", for example. "(Meth) acrylic-acid copolymer polyflow No. by Kyogisha Co., Ltd. make. 57, `` No. 90 "and the like.

In the said surfactant, since the removal of the photosensitive paste layer of an unexposed part at the time of image development is easy, nonionic surfactant is preferable, polyoxyethylene aryl ether is more preferable, and the compound represented by following General formula (1) This is preferred.

In Formula 1, R ¹ is an alkyl group having 1 to 5 carbon atoms, preferably a methyl group, p is an integer of 1 to 5, s is an integer of 1 to 5, preferably 2, t is 1 to 100 Integer, Preferably it is an integer of 10-20.

As said fatty acid, For example, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelagonic acid, lauric acid, myristic acid, pentadecyl acid, palmitic acid, palmitoyl acid, margaric acid, Stearic acid, oleic acid, basenic acid, linoleic acid, linolenic acid, nonadecanoic acid, arachidic acid, arachidonic acid, behenic acid, lignocelenic acid, nerbonic acid, serotic acid, montanic acid, melisic acid and the like.

The content of the dissolution accelerator in the photosensitive paste composition of the present invention is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, particularly preferably based on 100 parts by weight of the alkali-soluble resin (C). 0.1 to 10 parts by weight. When content of a dissolution promoter exists in the said range, the composition excellent in the solubility to a developing solution is obtained.

<Production of Photosensitive Paste Composition>

The photosensitive paste composition of this invention is an aluminum powder (A), alkali-soluble resin (C), a polyfunctional (meth) acrylate (D), and a photoinitiator (E), and the glass powder (B) used as needed. The above-mentioned various components, such as an organic solvent, are combined so that it may become a predetermined composition ratio, and it manufactures by mixing and disperse | distributing uniformly with a triaxial roll or a kneader.

Although the viscosity of the photosensitive paste composition of this invention can be suitably adjusted with the addition amount of an inorganic particle, a thickener, an organic solvent, a plasticizer, and a precipitation inhibitor, the range is preferably 100-500000 cps (centi poise). .

[Pattern Forming Method]

The pattern formation method of this invention is the process of forming the photosensitive paste layer containing the said photosensitive paste composition on a board | substrate (photosensitive paste layer formation process), and the process of exposing the said photosensitive paste layer to form the latent image of a pattern (exposure). Process), a process of developing the photosensitive paste layer to form a pattern (development process), and a process of baking the pattern (firing process).

<Photosensitive Paste Layer Forming Step>

In this step, a photosensitive paste layer containing the photosensitive paste composition is formed on a substrate. As a formation method of the photosensitive paste layer, the method of apply | coating the said photosensitive paste composition on a board | substrate to form a coating film, and drying the said coating film, etc. are mentioned, for example.

As a method of apply | coating the said photosensitive paste composition on a board | substrate, it will not specifically limit, if it is a method which can form a coating film with a large film thickness (for example, 20 micrometers or more) and excellent in uniformity efficiently. For example, 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 apparatus. The screen printing method, and the like.

The drying conditions of a coating film may be adjusted suitably so that the residual ratio of the organic solvent after drying may be less than 2 weight%, for example, it is about 0.5 to 60 minutes at the drying temperature of 50-150 degreeC.

The thickness of the photosensitive paste layer formed as mentioned above becomes like this. Preferably it is 3-300 micrometers, More preferably, it is 5-200 micrometers. Moreover, the application | coating of the photosensitive paste composition is repeated n times, and the laminated body which has an n layer (n represents the integer of 2 or more) photosensitive paste layer can also be formed.

Exposure process

After forming a photosensitive paste layer on a board | substrate by the said photosensitive paste layer forming process, it exposes using an exposure apparatus. As exposure is performed by normal photolithography, the method of mask exposure using a photomask can be employ | adopted. Although the exposure pattern of an exposure mask differs according to the objective, it is a stripe or grating of 10-500 micrometers width, for example.

Moreover, the method of drawing directly with a red or blue visible light laser beam, an Ar ion laser, etc. can also be used, without using a photomask.

The surface of the photosensitive paste layer is selectively irradiated (exposured) to radiation such as ultraviolet rays through a mask for exposure to form a latent image of a pattern on the paste layer. As an exposure apparatus, a parallel light exposure machine, a scattered light exposure machine, a stepper exposure machine, a proximity exposure machine, etc. can be used. Moreover, when exposing large area, a large area can be exposed by the exposure machine of a small exposure area by performing exposure, after conveying after apply | coating the photosensitive paste composition on board | substrates, such as a glass substrate.

Examples of the active light source used at the time of exposure include visible light, near ultraviolet light, ultraviolet light, electron beam, X-ray, laser light, and the like. Among these, ultraviolet light is preferable, and as the light source, for example, low pressure mercury lamp , High pressure mercury lamps, ultra high pressure mercury lamps, halogen lamps and the like can be used. Among these, an ultrahigh pressure mercury lamp is preferable.

Although exposure conditions change with application | coating thickness, it exposes for 0.05 to 1 minute using the ultrahigh pressure mercury lamp of 1-100 mW / cm <2> output, for example. In this case, by narrowing the wavelength region of exposure light using a wavelength filter, light scattering can be suppressed and pattern formation property can be improved. Specifically, pattern formation property can be improved using the filter which cuts the light of i line | wire (365 nm), or the filter which cuts the light of i line | wire and h line (405 nm).

Development Process

After the exposure, the photosensitive paste layer is developed by using the solubility difference with respect to the developer of the photosensitive portion and the non-photosensitive portion to form a pattern. Developing methods (e.g., immersion method, rocking method, shower method, spray method, puddle method, brush method, etc.) and developing process conditions (e.g., type, composition, concentration, developing time, developing temperature, etc. of developer) What is necessary is just to select and set suitably according to the kind of silver photosensitive paste layer.

As the developing solution used in the developing step, an organic solvent capable of dissolving an organic component in the photosensitive paste layer can be used. Moreover, water can also be added to the said organic solvent in the range in which the solvent power does not disappear. When the compound which has acidic groups, such as a carboxyl group, is interposed in the photosensitive paste layer, it can develop with aqueous alkali solution.

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

Examples of the alkali aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, and lithium silicate. , Sodium silicate, potassium silicate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, ammonia aqueous solution, tetramethylammonium hydroxide, trimethylhydroxyethyl Ammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine, diethanolamine, triethanolamine, and the like. have.

The concentration of the alkali 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 portion is not removed. If the alkali concentration is too high, the pattern portion may be peeled off and the insoluble portion may be corroded. Moreover, it is preferable in process control that image development temperature at the time of image development is performed at 20-50 degreeC.

The said alkali aqueous solution may contain additives, such as a nonionic surfactant and an organic solvent. In addition, after the image development process by alkaline developing solution is performed, the water washing process is performed normally.

<Firing process>

The firing atmosphere varies depending on the photosensitive paste composition and the type of substrate, but the firing atmosphere is baked in an atmosphere such as air, ozone, nitrogen, or hydrogen. As a kiln, a batch type kiln and a belt type continuous kiln can be used.

In the firing treatment conditions, since the organic material in the photosensitive paste layer remaining portion needs to be lost, the firing temperature is usually 300 to 1000 ° C and the firing time is 10 to 90 minutes. For example, when pattern-forming on a glass substrate, it bakes by hold | maintaining for 10 to 60 minutes at the temperature of 350-600 degreeC.

By the pattern formation method of this invention including these processes, members for display panels, such as an electrode, the circuit pattern of an electronic component, the wiring pattern of a solar cell member, etc. can be formed. In addition, a 50-300 degreeC heating process can also be introduce | transduced in the said process of photosensitive paste layer formation, exposure, image development, and baking for the purpose of drying or preliminary reaction.

[Manufacturing methods, such as members for FPDs]

By the pattern formation method of this invention including the said process, FPD members, such as an electrode, the circuit pattern of an electronic component, the wiring pattern of a solar cell member, etc. can be formed. Such a method for producing the FPD member of the present invention is suitable for a method for producing a PDP.

Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited at all by these Examples. In addition, "part" and "%" in an Example and a comparative example represent "weight part" and "weight%", respectively, unless there is particular notice.

First, the measuring method and evaluation method of a physical property are demonstrated.

[Measurement method of 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 of polystyrene conversion measured by gel permeation chromatography (GPC) ("HLC-8220GPC" manufactured by Tosoh Corporation). In addition, GPC measurement was performed on the conditions of the tetrahydrofuran (THF) solvent and the measurement temperature of 40 degreeC using "TSKguardcolumn SuperHZM-M" by Toso Corporation as a GPC column.

[Evaluation Method of Electrical Resistance Measurement]

The volume resistance [μΩ · cm] is formed by coating and baking the photosensitive paste composition on the glass substrate to form a film having a thickness of 10 μm on the glass substrate, and using “Resistivity Proccessor ModelΣ-5” manufactured by NPS Corporation. Evaluated.

[Evaluation Method of Pattern After Development and After Firing]

The test piece after image development and the baking was cut | disconnected, and the pattern cut surface was observed with the scanning electron microscope ("S4200" by Hitachi Seisakusho), the width and height of the pattern were measured, and each evaluated by the following reference | standard. In addition, a desired standard is 50 micrometers in width of a pattern, 10 micrometers in height, and 100 micrometers in space | intervals.

A: of desired specification

B: Within ± 5% of the desired specification

C: exceeding ± 5% from the desired specification within ± 10%

D: exceeding ± 10% from the desired specification

-: Unable to evaluate because of pattern peeling off

[Evaluation of Pattern Adhesion After Firing]

About the test piece after baking, adhesive evaluation of the pattern and the glass substrate which is a support body was performed as follows. In addition, the desired standard is 50 micrometers in width of a pattern, 10 micrometers in height, and 100 micrometers in spacing.

The cellophane tape (trademark: Nichiban Co., Ltd.) was thermocompression-bonded to the support surface constituting the test piece by a heating roller. In the crimping conditions, 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, the cellophane tape (registered trademark: Nichiban Co., Ltd.) was transferred to and adhered to the surface of the support. The adhesiveness of the pattern was evaluated by peeling this cellophane tape (trademark: Nichiban Co., Ltd. product) from a support body.

○: no pattern peeling

×: There is a pattern peeling

Synthesis Example 1

45 parts of 2-methacryloyloxyethyl phthalic acid, 55 parts of benzyl methacrylate, 1 part of azobisisobutyronitrile (AIBN), pentaerythritol tetrakis (3-mercaptopropionic acid) (Sakai Chemical Co., Ltd. 5 parts) was put into the autoclave with a stirrer, and it stirred under nitrogen atmosphere until it became uniform in 150 parts of terpineol.

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

Synthesis Example 2

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

Synthesis Example 3

25 parts of methacrylic acid, 75 parts of benzyl methacrylate, 1 part of azobisisobutyronitrile (AIBN) and 5 parts of novma NSD (manufactured by Nippon Yushi Co., Ltd.) were placed in an autoclave with a stirrer and under a nitrogen atmosphere. It stirred until it became uniform in 150 parts of terpineol.

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

Synthesis Example 4

25 parts of methacrylic acid, benzyl methacrylate 75 parts, azobisisobutyronitrile (AIBN) 1 part, pentaerythritol tetrakis (3-mercaptopropionic acid) (manufactured by Sakai Chemical Industries, Ltd.) 5 parts It was put into an autoclave with and stirred under nitrogen atmosphere until it became uniform in 150 parts of terpineol.

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

Synthesis Example 5

25 parts of methacrylic acid, 75 parts of benzyl methacrylate, 1 part of azobisisobutyronitrile (AIBN), 5 parts of pentaerythritol tetrakis (3-mercaptopropionic acid) (manufactured by Sakai Chemical Co., Ltd.) It was put into an autoclave with and stirred in a nitrogen atmosphere until it became uniform in 150 parts of propylene glycol monomethyl ether.

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

[Production of Photosensitive Resin Component]

Photosensitive resin components (1)-(6) of the composition shown in following Table 3 were manufactured.

Example 1

The aluminum powder A1 (16 g) shown in following Table 1, the glass powder B1 (2 g) shown in following Table 2, and the photosensitive resin component (1) (40 g) shown in Table 3 are knead | mixed with a kneading machine, and the photosensitive paste composition ( Hereinafter also referred to as "photosensitive paste").

The photosensitive paste was printed to a test piece (150 mm x 150 mm x 2.8 mm) on a glass substrate with a size of 100 mm2 using a 325 reticulated screen, maintained at 100 ° C for 10 minutes, dried, and then photosensitive paste. A layer was formed.

Next, using the negative chrome mask (pattern width 50 micrometers, pattern space | interval 100 micrometers), the photosensitive paste layer was ultraviolet-ray-exposed from the upper surface by the ultrahigh pressure mercury lamp of 25 mW / cm <2> output. The exposure amount was 1000 mJ / cm 2.

Next, it developed by adding the 0.5% aqueous solution of sodium carbonate hold | maintained at 23 degreeC to the photosensitive paste layer after exposure for 60 second by shower. Thereafter, water was washed with a shower spray to remove the uncured portion to form a lattice-shaped cured pattern on the glass substrate. The hardening pattern after this image development was evaluated by the said evaluation method. The results are shown in Table 4 below.

Next, the obtained hardening pattern was baked at 580 degreeC for 30 minutes, and the electrode pattern was formed. The electrode pattern after this baking was evaluated by the said evaluation method. The results are shown in Table 4.

[Examples 2 to 15]

Except having manufactured the photosensitive paste using the aluminum powder, glass powder, and photosensitive resin component shown in Table 4, it carried out similarly to Example 1, and formed the photosensitive paste layer, the hardening pattern, and the electrode pattern on the glass substrate one by one. Next, the hardening pattern and the electrode pattern were evaluated by the said evaluation method. The results are shown in Table 4. In addition, the film thickness of the photosensitive paste layer was in the range of 10 micrometer +/- 1micrometer anywhere in Examples 1-15.

Example 16

Except having manufactured the photosensitive paste using the aluminum powder, glass powder, and photosensitive resin component shown in Table 4, it carried out similarly to Example 1, and formed the photosensitive paste layer, the hardening pattern, and the electrode pattern on the glass substrate one by one. Next, the hardening pattern and the electrode pattern were evaluated by the said evaluation method. The results are shown in Table 5 below. In addition, the film thickness of the photosensitive paste layer existed in the range of 10 micrometer +/- 1micrometer.

Example 17

Aluminum powder A1 (16 g) shown in Table 1, glass powder B1 (2 g) shown in Table 2, and photosensitive resin component (6) (82 g) shown in Table 3 were kneaded with a kneading machine to form a photosensitive paste composition (hereinafter referred to as "photosensitive Paste ".

As a support film, two polyethylene terephthalate (PET) films (200 mm in width, 30 m in length, 50 micrometers in thickness) which carried out the mold release process were prepared previously.

Next, on one support film, the said photosensitive paste was apply | coated with a roll coater, a coating film was formed, the formed coating film was dried at 100 degreeC for 5 minutes, and the solvent was removed, and the photosensitive paste layer of thickness 10micrometer was formed. .

Next, the other support film was bonded with the said photosensitive paste layer, and was thermocompressed with the heating roller. The crimping conditions made the surface temperature of a heating roller 90 degreeC, the roll pressure 4 kg / cm <2>, and the moving speed of a heating roller the speed | rate 0.5 m / min. In this way, a transfer film having a photosensitive paste layer (thickness 10 μm) was produced.

Next, one support film is peeled off, the said photosensitive paste layer is superposed on the surface of the glass substrate which is a test piece (150 * 150 * 2.8mm), and the remaining support film is peeled off, and then the photosensitive paste layer is heated by a heating roller. Thermocompression bonding. In the crimping conditions, the surface temperature of the heating roller was 90 ° C, the roll pressure was 4 kg / cm 2, and the moving speed of the heating roller was 0.5 m / min.

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

Next, using the negative chrome mask (pattern width 50 micrometers, pattern space | interval 100 micrometers), the photosensitive paste layer was ultraviolet-ray-exposed from the upper surface by the ultrahigh pressure mercury lamp of 25 mW / cm <2> output. The exposure amount was 500 mJ / cm 2.

Next, it developed by adding the 0.5% aqueous solution of sodium carbonate maintained at 23 degreeC to the photosensitive paste layer after exposure for 60 second with a shower. Thereafter, water washing was performed using a shower spray, and the uncured portion was removed to form a lattice-shaped exposure pattern on the glass substrate. The exposure pattern after this image development was evaluated by the said evaluation method. The results are shown in Table 4.

Next, the obtained exposure pattern was baked at 580 degreeC for 30 minutes, and the electrode pattern was formed. The electrode pattern after this baking was evaluated by the said evaluation method. The results are shown in Table 4.

Example 18

Except having manufactured the photosensitive paste using the aluminum powder A1 (45g) shown in Table 1, the glass powder B1 (5g) shown in Table 2, and the photosensitive resin component (5) (50g) shown in Table 3, In the same manner as in 1, a photosensitive paste layer, a cured pattern, and an electrode pattern were sequentially formed on the glass substrate. Next, the hardening pattern and the electrode pattern were evaluated by the said evaluation method. The results are shown in Table 4.

Example 19

Except having manufactured the photosensitive paste using the aluminum powder A1 (35g) shown in Table 1, the glass powder B1 (20g) shown in Table 2, and the photosensitive resin component (5) (45g) shown in Table 3, In the same manner as in 1, a photosensitive paste layer, a cured pattern, and an electrode pattern were sequentially formed on the glass substrate. Next, the hardening pattern and the electrode pattern were evaluated by the said evaluation method. The results are shown in Table 4.

Example 20

Except having manufactured the photosensitive paste using the aluminum powder A1 (20g) shown in Table 1, the glass powder B1 (30g) shown in Table 2, and the photosensitive resin component (5) (50g) shown in Table 3, In the same manner as in 1, a photosensitive paste layer, a cured pattern, and an electrode pattern were sequentially formed on the glass substrate. Next, the hardening pattern and the electrode pattern were evaluated by the said evaluation method. The results are shown in Table 4.

TMP: trimethylolpropane (propion oxide modified) triacrylate

MTPMP: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propan-1-one

DETX: 2,4-diethyl thioxanthone

BHHD: 1,7-bis (4-hydroxyphenol) -1,6-heptadiene-3,5-dione

TNOL: Terpineol

PGME: Propylene Glycol Monomethyl Ether

As shown in Table 4, Examples 1-6, 10-12, 17-20 were especially excellent as pattern evaluation after image development and after baking. Examples 7 to 9, 13, 14 and 16 were good. Example 15 was slightly good. In addition, as evaluation of a volume resistance, Examples 1-15 and 17-20 were in the range of 50-200 microohm * cm. Example 16 was in the range of 400-600 micrometer * cm.

Comparative Example 1

Except having manufactured the photosensitive paste using the aluminum powder, glass powder, and photosensitive resin component shown in Table 5, it carried out similarly to Example 1, and formed the photosensitive paste layer, the hardening pattern, and the electrode pattern on the glass substrate one by one. Next, the hardening pattern and the electrode pattern were evaluated by the said evaluation method. The results are shown in Table 5.

As shown in Table 5, in the evaluation of the pattern after development and after firing, in Comparative Example 1, aggregation or gelation was expressed and could not be evaluated. In addition, peeling of the electrode pattern was observed. As evaluation of volume resistance, the comparative example 1 was in the range of 400-600 micrometer * cm.

1 is a schematic diagram showing a cross-sectional shape of an AC plasma display panel.

2 is a schematic diagram showing a cross-sectional shape of a typical field emission display.

<Explanation of symbols for the main parts of the drawings>

101: glass substrate

102: glass substrate

103: rear bulkhead

104: transparent electrode

105: bus electrode

106: address electrode

107: fluorescent material

108: dielectric layer

109: dielectric layer

110: protective layer

111: front bulkhead

201: glass substrate

202: glass substrate

203: insulating layer

204: transparent electrode

205 emitter

206: cathode electrode

207: phosphor

208: gate

209: spacer

Claims (8)

Aluminum powder (A) having a 50 wt% particle size (D50) of 2.0 to 20.0 μm, except for the metal-coated aluminum powder, Alkali soluble resin (C), Polyfunctional (meth) acrylates (D), and Photopolymerization Initiator (E) A photosensitive paste composition comprising a. Content of the said aluminum powder (A) is 15 to 70 weight% with respect to the whole photosensitive paste composition, The photosensitive paste composition of Claim 1 characterized by the above-mentioned. The said alkali-soluble resin (C) is an at least 1 sort (s) of alkali-soluble functional group chosen from carboxyl group-containing monomers, hydroxyl-containing monomers, and phenolic hydroxyl-containing monomers in the whole structural unit. It is resin containing 5 to 90 weight% of structural units derived from a containing monomer (C1), The photosensitive paste composition characterized by the above-mentioned. The acid value of the said alkali-soluble resin (C) is 20-200 mgKOH / g, The photosensitive paste composition of Claim 1 or 2 characterized by the above-mentioned. The photosensitive paste composition according to claim 1 or 2, further comprising a glass powder (B) having a 50 wt% particle size (D50) of 0.2 to 4.0 µm. The photosensitive paste composition according to claim 5, wherein the glass powder (B) contains a glass powder having a softening point of 350 to 700 ° C in a proportion of 0.5 to 15% by weight based on the entire photosensitive paste composition. The said aluminum powder (A) is aluminum powder in which fatty acid is contained, The photosensitive paste composition of Claim 1 or 2 characterized by the above-mentioned. The process of forming the photosensitive paste layer containing the photosensitive paste composition of Claim 1 or 2 on a board | substrate, Exposing the paste layer to form a latent image of the pattern; Developing the paste layer to form a pattern, and Firing the pattern Pattern forming method comprising a.

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