JP2000010268A - Photosensitive paste, production of plasma display using the same, and member for plasma display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive paste that enables high aspect ratio and high precision patterning at a low cost. SOLUTION: The photosensitive paste contains inorg. fine particles and a photosensitive org. component as essential components and the photosensitive org. component contains a compd. represented by the formula R1R3N-L-NR2R4, wherein R1 and R2 are each a substituent having an ethylenically unsatd. group, R3 and R4 are each selected from among a substituent having an ethylenically unsatd. group, H, 1-20C alkyl, aryl or aralkyl, R3 and R4 may be mutually the same or different and L is a divalent combining group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The photosensitive paste of the present invention is
It is used for pattern processing and formation of various displays such as plasma displays and plasma addressed liquid crystal displays, circuit materials, and the like.

[0002]

2. Description of the Related Art In recent years, miniaturization and high definition of circuit materials and displays have been advanced, and accordingly, a technique of pattern processing has been desired. In particular, a material capable of patterning an inorganic material such as glass with high precision and a high aspect ratio is desired for forming a partition of a plasma display.

Conventionally, when patterning an inorganic material, screen printing using a paste composed of an inorganic powder and an organic binder is often used. However, screen printing has a drawback that a pattern with high accuracy cannot be formed.

As a method for solving this problem, Japanese Patent Laid-Open No.
Japanese Patent Application Laid-Open Nos. 296534/1990, 165538/1993, and 354292/1993 propose a method of forming a pattern by a photolithography technique using a photosensitive paste. However, since the sensitivity and resolution of the photosensitive paste are low, a high aspect ratio and high definition partition cannot be obtained. For example, when patterning a material having a thickness exceeding 80 μm, a plurality of processing steps (coating , Exposure and development).

[0005]

DISCLOSURE OF THE INVENTION The present inventors have intensively studied a photosensitive paste which enables high aspect ratio and high definition pattern processing in a single processing step. In the case of processing a pattern having a thickness, the sensitivity is low and a large amount of exposure is required, so that the workability is poor.

[0006]

Means for Solving the Problems The present inventors have made it possible to incorporate a specific photopolymerizable monomer into a photosensitive paste containing inorganic fine particles and a photosensitive organic component as essential components.
The inventors have found that a photosensitive paste with high sensitivity can be obtained, and have completed the present invention based on this finding.

That is, the present invention provides a photosensitive paste containing inorganic fine particles and a photosensitive organic component as essential components, wherein the photosensitive organic component contains a compound represented by the following general formula (I). Achieved by a photosensitive paste. (I) R ¹ R ³ NL-NR ² R ^{4 wherein} R ¹ and R ² are substituents having an ethylenically unsaturated group, and R ³ and R ⁴ are ethylenically unsaturated groups , A hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, and an aralkyl group, which may be the same or different. L represents a divalent linking group. Further, the present invention is a method for manufacturing a plasma display, comprising a step of forming a pattern by photolithography after applying a photosensitive paste on a substrate and drying, and baking the pattern to form a partition, A method for manufacturing a plasma display, comprising using the above-mentioned photosensitive paste as the photosensitive paste.

The present invention also provides a member for a plasma display, which is manufactured using the above-mentioned photosensitive paste.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive paste of the present invention comprises inorganic fine particles and a photosensitive organic component, and is formed by firing after forming a pattern using photolithography to form an inorganic pattern.

The inorganic fine particles in the present invention are fine particles of glass or ceramics, and are particularly useful when glass powder is used.

As the glass powder, the glass transition point 430
When the paste contains glass powder having a softening point of 500 ° C. and a softening point of 470-580 ° C. in an amount of 50% by weight or more, pattern processing can be performed on a substrate used for a normal display.

By mixing the metal oxide component such that it has such a glass transition point and softening point and the refractive index of the glass particles is 1.5 to 1.65, the refractive index of the organic component can be improved. And high-precision pattern processing by suppressing light scattering becomes possible. For example, silicon oxide: 22, aluminum oxide: 23, boron oxide: 33,
A glass powder composed of lithium oxide: 9, magnesium oxide: 7, barium oxide: 4, and zinc oxide 2 (% by weight) has a glass transition point of 490 ° C, a softening point of 528 ° C, and refraction at a g-line wavelength (436 nm). Rate: 1.59, which satisfies the conditions for use as the inorganic fine particles of the present invention.

The preferred glass powder as the photosensitive paste of the present invention has the following composition. Lithium oxide: 3 to 10% by weight Silicon oxide: 10 to 30% by weight Boron oxide: 20 to 40% by weight Barium oxide: 2 to 15% by weight Aluminum oxide: 10 to 25% by weight Contains 3 to 10% by weight of lithium oxide The use of glass powder not only facilitates the control of the thermal softening temperature and the coefficient of thermal expansion, but also makes it possible to lower the average refractive index of the glass, thereby making it easier to reduce the refractive index difference from the organic component. The addition amount of the alkali metal oxide is preferably 10% by weight or less, more preferably 8% by weight or less, in order to improve the stability of the paste.

In the above composition, sodium oxide or potassium oxide may be used instead of lithium oxide, but lithium oxide is preferred in view of the stability of the paste.
In the case of using potassium oxide, there is an advantage that the refractive index can be controlled with a relatively small amount of addition. Therefore, among the alkali metal oxides, addition of lithium oxide and potassium oxide is effective. In that case, alkali metal oxides should be 3
It is preferable to use glass powder containing from 10 to 10% by weight.

It is preferable that silicon oxide is blended in the range of 10 to 30% by weight, and if it is less than 10% by weight, the denseness, strength and stability of the glass layer are reduced, and the thermal expansion coefficient is out of a desired value. , A mismatch with a glass substrate is likely to occur. Further, by setting the content to 30% by weight or less, there is an advantage that the softening point is lowered and baking on a glass substrate becomes possible.

It is preferable that boron oxide is blended in the range of 20 to 40% by weight. If it exceeds 40% by weight, the stability of the glass will be reduced. Boron oxide is glass powder of 800 to 12
Since it is melted at a temperature around 00 ° C and the baking temperature of the glass paste is high even when silicon oxide is large, it does not impair the electrical, mechanical and thermal properties such as electrical insulation, strength, coefficient of thermal expansion and denseness of the insulating layer. To control the baking temperature in the range of 540 to 610 ° C. If it is less than 20% by weight, the strength of the insulating layer is reduced, and the stability of the glass is reduced.

Preferably, barium oxide is blended in the range of 2 to 15% by weight. If it is less than 2% by weight, it is difficult to control the glass baking temperature and the electrical insulation.
On the other hand, if the content exceeds 15% by weight, the stability and the denseness of the glass layer decrease.

It is preferable that aluminum oxide is blended in the range of 10 to 25% by weight. Aluminum oxide is added to increase the strain point of the glass. If it is less than 10% by weight, the strength of the glass layer is reduced. If it exceeds 25% by weight, the heat resistance temperature of the glass becomes too high, and it is difficult to bake the glass on the glass substrate. Further, it becomes difficult to obtain a dense insulating layer at a temperature of 600 ° C. or lower.

It is preferable that zinc oxide is blended in the range of 1.5 to 10% by weight. If it is less than 1.5% by weight, there is no effect on improving the denseness of the insulating layer. If it exceeds 10% by weight, the temperature for baking on the glass substrate becomes too low to control, and the insulation resistance is undesirably low.

It is preferable that calcium oxide is blended in the range of 2 to 10% by weight. Added to help melt the glass and control the coefficient of thermal expansion. If it is less than 2% by weight, the strain point becomes too low.

It is preferable that magnesium oxide is blended in the range of 1 to 10% by weight. Magnesium oxide is added to facilitate melting of the glass and to control the coefficient of thermal expansion. If it exceeds 10% by weight, the glass tends to be devitrified, which is not good.

It is preferable that the glass powder does not contain sodium oxide, potassium oxide, yttrium oxide or the like which deteriorates the discharge characteristics of the plasma. Even when it is contained, it is at most 5% by weight.

The glass powder may contain titanium oxide, zirconium oxide and the like, but the amount is preferably less than 2% by weight. Zirconium oxide is effective in controlling the softening point, transition point and electrical insulation of glass.

As a method for producing glass powder, for example, raw materials such as lithium oxide, silicon oxide, aluminum oxide,
Boron oxide, barium oxide, zinc oxide, and the like are mixed so as to have a predetermined composition, melted at 900 to 1200 ° C., quenched, glass frit, and pulverized.
Make a fine powder of μm. As a raw material, a high-purity carbonate, oxide, hydroxide, or the like can be used. In addition, depending on the type and composition of the glass powder, ultra-high purity alkoxide or organometallic raw material of 99.99% or more is used. It is preferable because a high-strength insulating layer having few pores can be obtained.

The particle diameter of the glass powder used in the above is selected in consideration of the shape of the pattern to be produced, but the powder has a particle diameter of 50% by weight (average particle diameter) of 2 to 2.
It is necessary that the thickness be 3.5 μm and the top size be 15 μm or less. Further, when the 10% by weight particle size is 0.6 to 1.5.
μm, 90% by weight particle size 4-8 μm, specific surface area 1.5
It preferably has a density of up to ^2.5 m ² / g. More preferably, the average particle size is 2.5 to 3.5 μm, and the specific surface area is 1.
7 to 2.4 m ² / g. Within this range, light is sufficiently transmitted at the time of ultraviolet exposure, and a partition pattern with a small line width difference between the upper and lower portions can be obtained. If the average particle size is 2.0 μm or less and the specific surface area exceeds 2.5 m ² / g, the powder becomes too fine and light is scattered at the time of exposure to cure the unexposed portion, which is not preferable.

In the present invention, the photosensitive organic component is a photosensitive organic component (a part obtained by removing the inorganic component from the paste) in the photosensitive paste, and preferably contains 5 to 50% by weight of the paste. .

The organic component is a photosensitive component and a binder selected from at least one of a photosensitive monomer, a photosensitive oligomer and a photosensitive polymer, the ultraviolet absorber and the antioxidant, an organic dye, a photopolymerization initiator, It is constituted by adding an additive component such as a sensitizer, a sensitization aid, a plasticizer, a thickener, an organic solvent, a dispersant, and an organic or inorganic suspending agent as required.

In order to obtain a highly sensitive photosensitive paste, the photosensitive organic component of the present invention includes a compound represented by the following formula (I). (I) R ¹ R ³ NL-NR ² R ^{4 wherein} R ¹ and R ² are substituents having an ethylenically unsaturated group, and R ³ and R ⁴ are ethylenically unsaturated groups , A hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, and an aralkyl group, which may be the same or different. L represents a divalent linking group. In R ^{1 to} R ⁴ , some of the hydrogen atoms may be substituted with a substituent. As such a substituent, a C 1 -C 1
6, an alkyl group, a halogen atom, a hydroxyl group, and an aryl group. Preferably, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
sec-butyl group, hydroxypropyl group, chloromethyl group, bromomethyl group, phenyl group, p-hydroxyphenyl group, p-bromophenyl group, p-tolyl group, o-
Examples include a tolyl group and a benzyl group.

The divalent linking group L preferably has the general formula-
(L ¹ ) _p- (L ² ) _q- . In the formula, L ¹ is selected from a cyclic or acyclic alkylene having 1 to 20 carbon atoms, an arylene, and an alkylene, and, like R ^{1 to} R ⁴ , an alkyl group having 1 to 6 carbon atoms. , A halogen atom, a hydroxyl group, an aryl group, or the like. L ² is
^{-O-E 1 -, - S} -E 2 -, - NH-E 3 -, - CO-
^{O-E 4 -, - SO} 2 -NH-E 5 - , etc., E ^1, E ^2,
E ³ , E ⁴ and E ⁵ are selected from the above alkylene, arylene and aralkylene. p represents an integer of 1 or more, and q represents 0 or an integer of 1 or more. More preferably,
p is 1, L ¹ is alkylene having 1 to 6 carbon atoms, L ²
It is -O-E ¹ -, or -NH-E ³ - a, E ^1, E ³ is alkylene having 1 to 6 carbon atoms.

Examples of the substituent having an ethylenically unsaturated group include those represented by the following general formulas (II), (III) and (IV). ^{_{(II) CH 2 = CR 5}} -A- (L 3) a -CHOH-CH 2 - (III) CH 2 = CR 5 - (A) b - (L 3) a -SO 2 - (IV) CH 2 _{^{= CR 5 - (a) b}} - (L 3) a -CO- wherein, R ⁵ is a hydrogen atom or a methyl group. A is
—CO—O—, —CO—NH—, or a substituted or unsubstituted phenylene group. L ³ has the same definition as L described above. a and b represent 0 or 1. Above all, CH ₂ = CC
H ₃ COOCH ₂ CHOHCH ₂ - is most preferred.

To prepare compound (I), glycidyl (meth) acrylate having an ethylenically unsaturated group,
(Meth) acrylic acid chloride, (meth) acrylic anhydride and the like may be reacted with an amino compound. The amount of the compound containing an ethylenically unsaturated group to be added is at least 2 moles per mole of the amino compound, and the highest is the number of moles capable of reacting with all active hydrogens of the amino compound. A plurality of ethylenically unsaturated group-containing compounds may be used as a mixture.

Specific examples of the compound (I) are shown in Table 1, but are not limited thereto. These compounds may be used as a mixture. In order to obtain an appropriate exposure dose, the amount of compound (I) to be added should be 10% in the photosensitive organic component.
Preferably it is ~ 80% by weight.

[0033]

[Table 1]

In the present invention, an ethylenically unsaturated group-containing monomer other than the monomer represented by the general formula (I) can be used, if necessary. Examples of such monomers include monomers having one or more photopolymerizable (meth) acrylate groups or allyl groups. Specific examples thereof include acrylic or methacrylic acid esters of alcohols (eg, ethanol, propanol, hexanol, octanol, cyclohexanol, glycerin, trimethylolpropane, pentaerythritol, etc.), and carboxylic acids (eg, acetic acid,
Propionic acid, benzoic acid, acrylic acid, methacrylic acid,
Reaction products of succinic acid, maleic acid, phthalic acid, tartaric acid, citric acid, etc.) with glycidyl acrylate, glycidyl methacrylate, allyl glycidyl, or tetraglycidyl methaxylylenediamine; amide derivatives (eg, acrylamide, methacrylamide, N-methylolacrylamide, methylenebisacrylamide, etc.), and a reaction product of an epoxy compound and acrylic acid or methacrylic acid. Further, in the polyfunctional monomer, the unsaturated group is acryl, methacryl,
Allyl groups may be present as a mixture. These may be used alone or in combination.

The photopolymerization initiator used in the present invention is selected from those generating radical species. Specific examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, 4,4-dichlorobenzophenone, Benzoyl-4-methylphenyl ketone, dibenzyl ketone,
Fluorenone, 2,3-diethoxyacetophenone,
2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone , Diethylthioxanthone, benzyl, benzyldimethyl ketal, benzylmethoxyethyl acetal, benzoin,
Benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone,
2-aminoanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) )
-4-methylcyclohexanone, 2-phenyl-1,2
-Butadione-2- (o-methoxycarbonyl) oxime, 1-phenylpropanedione-2- (o-ethoxycarbonyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime,
-Methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, naphthalenesulfonyl chloride, quinoline sulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benz Thiazole disulfide, triphenylphosphine, camphorquinone,
Examples include a combination of a photoreducing dye such as carbon tetrabromide, tribromophenylsulfone, benzoyl peroxide and eosin, and methylene blue with a reducing agent such as ascorbic acid and triethanolamine.

In the present invention, one or more of these can be used. The photopolymerization initiator is added in a range of 0.05 to 10% by weight, more preferably 0.1 to 10% by weight, based on the photosensitive component. If the amount of the polymerization initiator is too small, the photosensitivity becomes poor, and if the amount of the photopolymerization initiator is too large, the residual ratio of the exposed portion may be reduced.

By using a sensitizer together with the photopolymerization initiator, the sensitivity can be improved and the wavelength range effective for the reaction can be extended.

Specific examples of the sensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone,
3-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-dimethylaminobenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone, 4,4-bis (diethylamino) benzophenone,
4,4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) iso Naphthothiazole, 1,3-bis (4-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4-dimethylaminobenzal) acetone, 1,3-carbonylbis (4-diethylaminobenzal) acetone, 3,3-carbonylbis (7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5 -Benzoi Thiotetrazole, such as 1-phenyl-5-ethoxycarbonyl-thiotetrazole the like.

In the present invention, one or more of these can be used. Some sensitizers can also be used as photopolymerization initiators. When a sensitizer is added to the photosensitive paste of the present invention, the amount is usually 0.05 to 10% by weight, more preferably 0.1 to 10% by weight, based on the photosensitive component. If the amount of the sensitizer is too small, the effect of improving the photosensitivity is not exhibited, and if the amount of the sensitizer is too large, the residual ratio of the exposed portion may be reduced.

As an organic component constituting the photosensitive paste, an oligomer or a polymer is used as a component that plays a role in improving the physical properties of a cured product formed by a photoreaction and adjusting the viscosity of the paste. The oligomer or polymer is obtained by polymerization or copolymerization of a component selected from compounds having a carbon-carbon double bond.

As a monomer to be copolymerized, the developability with an aqueous alkali solution after exposure can be improved by copolymerizing an unsaturated acid such as an unsaturated carboxylic acid. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof.

The polymer or oligomer having an acidic group such as a carboxyl group in the side chain thus obtained has an acid value (AV) of preferably from 50 to 180, more preferably from 70 to 140. When the acid value exceeds 180, the allowable development width becomes narrow. Further, when the acid value is 50 or less, the solubility of the unexposed portion in the developing solution is reduced, so that the developing solution concentration is increased, peeling occurs up to the exposed portion, and it is difficult to obtain a high-definition pattern. Become.

By adding a photoreactive group to a side chain or a molecular terminal to the polymer or oligomer described above, it can be used as a photosensitive polymer or oligomer having photosensitivity.

Preferred photoreactive groups are those having an ethylenically unsaturated group. As the ethylenically unsaturated group,
Examples include a vinyl group, an allyl group, an acryl group, and a methacryl group.

A method for adding such a side chain to an oligomer or a polymer is based on an ethylenically unsaturated compound having a glycidyl group or an isocyanate group or an acrylic acid, with respect to a mercapto group, an amino group, a hydroxyl group or a carboxyl group in the polymer. There is a method in which chloride, methacrylic chloride or allyl chloride is added to make an addition reaction.

Examples of the ethylenically unsaturated compound having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, glycidyl ether crotonic acid and glycidyl ether isocrotonic acid. .

Examples of the ethylenically unsaturated compound having an isocyanate group include (meth) acryloyl isocyanate and (meth) acryloylethyl isocyanate. The ethylenically unsaturated compound having a glycidyl group or an isocyanate group, acrylic acid chloride, methacrylic acid chloride or allyl chloride is used in an amount of 0.05 to 1 mol based on the mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. It is preferable to add an amount.

The present invention is characterized in that an organic component contains 10 to 90% by weight of an oligomer or polymer having a weight average molecular weight of 500 to 100,000 containing a carboxyl group and an unsaturated double bond in the molecule. .

When a binder component is required, polyvinyl alcohol, polyvinyl butyral,
A methacrylate polymer, an acrylate polymer, an acrylate-methacrylate copolymer, a butyl methacrylate resin, or the like can be used. It is also effective to increase the refractive index of the binder component to increase the refractive index of the photosensitive organic component.

In the present invention, it is important to add an antioxidant. The antioxidant has a radical chain inhibiting action, a triplet eliminating action, and a hydroperoxide decomposing action.

Since the photosensitive paste contains many glass microparticle components in a dispersed state, it is difficult to avoid light scattering inside the paste due to exposure light. Formation) is likely to occur. The walls of the pattern are desirably vertically cut and rectangular. Ideally, it is dissolved in the developer below a certain exposure amount, and insoluble in the developer above it. In other words, even when cured at a low exposure amount due to light scattering, it is dissolved in a developing solution, the thickening of the pattern shape and filling between the patterns are eliminated, and the range of resolution can be increased even when the exposure amount is increased.

When an antioxidant is added to the photosensitive paste, the antioxidant captures radicals and returns the energy state of the excited photopolymerization initiator and sensitizer to the ground state, thereby causing scattering by the scattered light. An excess photoreaction is suppressed, and a photoreaction occurs rapidly at an exposure amount that cannot be suppressed by an antioxidant, so that the contrast between dissolution and insolubility in a developer can be increased.

Specifically, p-benzoquinone, naphthoquinone, para-xyloquinone, para-toluquinone, 2,6
-Dichloroquinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicaproxy-p-benzoquinone, hydroquinone, pt-butylcatechol, 2,5-dibutylhydroquinone, mono-t-butylhydroquinone,
2,5-di-t-amylhydroquinone, di-t-butyl paracresol, hydroquinone monomethyl ether,
α-naphthol, hydrazine hydrochloride, trimethylbenzylammonium chloride, trimethylbenzylammonium oxalate, phenyl-β-naphthylamine, parabenzylaminophenol, di-β-naphthylparaphenylenediamine, dinitrobenzene, trinitrobenzene, picric acid, quinone Dioxime, cyclohexanone oxime, pyrogallol, tannic acid, triethylamine hydrochloride, dimethylaniline hydrochloride, cuperone,
(2,2′-thiobis (4-t-octylphenolate) -2-ethylhexylaminonickel- (II),
4,4'-thiobis- (3-methyl-6-t-butylphenol), 2,2'-methylenebis- (4-methyl-
6-t-butylphenol), 2,2'-thiobis-
(4-methyl-6-t-butylphenol), triethylene glycol-bis [3- (t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6
-Hexanediol-bis [(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,
Examples include, but are not limited to, 2,3-trihydroxybenzene. In the present invention, one or more of these can be used.

The amount of the antioxidant to be added is 0.1% in the paste.
It is in the range of 1 to 30% by weight, more preferably 0.5 to 20%. When the amount is less than these ranges, it is difficult to form a contrast of dissolution or insolubility in the developer, and when the amount is more than these ranges, the sensitivity of the photosensitive paste is reduced, and a large amount of exposure is required, or the degree of polymerization is reduced. As a result, the pattern shape cannot be maintained.

Further, by adding an ultraviolet absorber, scattered light inside the paste due to exposure light can be absorbed and scattered light can be reduced. Examples of the ultraviolet absorber include a benzophenone-based compound, a cyanoacrylate-based compound, a salicylic acid-based compound, a benzotriazole-based compound, an indole-based compound, and inorganic fine metal oxides.
Of these, benzophenone-based compounds, cyanoacrylate-based compounds, benzotriazole-based compounds, and indole-based compounds are particularly effective. Specific examples of these include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,
2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-
2'-carboxybenzophenone, 2-hydroxy-4
-Methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4- Dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4- (2-hydroxy-3-methacryloxy) propoxybenzophenone, 2- (2 ′
-Hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-
Butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl)
-5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-
4'-n-octoxyphenyl) benzotriazole,
2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, 2-ethyl-2-cyano-3,3-diphenyl acrylate, BO as an indole-based absorbent
Examples include, but are not limited to, NASORB UA-3901 (manufactured by Orient Chemical), BONASORB UA-3902 (manufactured by Orient Chemical), and SOM-2-0008 (manufactured by Orient Chemical). Further, a methacryl group or the like may be introduced into the skeleton of these ultraviolet absorbers and used as a reaction type. In the present invention, one or more of these can be used.

It should be noted that the transmission limit wavelength and the wavelength gradient width of the photosensitive paste film change depending on the amount of the ultraviolet absorber added. The transmission limit wavelength and wavelength slope width are
It is determined as follows according to JIS B7113. Film thickness 5
A wavelength at which the transmittance of the photosensitive paste film at 0 μm is 72% or more is a high transmission region, a wavelength corresponding to the limit is a transmission limit wavelength, and a wavelength at which the transmittance of the photosensitive paste film at a film thickness of 50 μm is 5% or less. A region is defined as an absorption region, and a wavelength corresponding to the limit is defined as an absorption limit wavelength. The interval between the transmission limit wavelength and the absorption limit wavelength is defined as the wavelength gradient width, and the wavelength corresponding to the middle point of the wavelength gradient width is defined as the transmission limit wavelength. The transmission limit wavelength and the wavelength gradient width can be measured using a general spectrophotometer.

The transmission limit wavelength is preferably 400 nm or more. More preferably, 400 nm or more and 436 n
m or less. Usually, the exposure used for the photolithography technique is performed using the g-line (436 nm), the h-line (405 nm), and the i-line (365 nm) of an ultra-high pressure mercury lamp. Absorption by a photosensitive compound (photopolymerization initiator or sensitizer) is too large, only the surface layer is exposed, and the lower layer is insufficiently cured. When the transmission limit wavelength is in this range, light having wavelengths near h-line and i-line can be absorbed, thereby increasing the transmittance of g-line and sufficiently curing the photosensitive paste to the lower layer. Also,
The transmission limit wavelength is in this range, and the wavelength gradient width is 5
When the thickness is 0 nm or less, the transmittance of only the wavelength near the g-line can be increased, which is more preferable.

The amount of the ultraviolet absorber added is 0.001 to 10% by weight in the paste, more preferably 0.005 to 10% by weight.
５5%. Beyond these ranges, the transmission limit wavelength and the wavelength gradient width change, and the ability to absorb scattered light is insufficient, the transmittance of exposure light is reduced, and the sensitivity of the photosensitive paste is reduced.

In the present invention, an organic dye can be added as a mark for exposure and development. By adding a dye and coloring, visibility is improved, and it becomes easy to distinguish a portion where the paste remains and a portion where the paste has been removed during development. The organic dye is not particularly limited, but preferably does not remain in the insulating film after firing. Specifically,] dyes, anthraquinone dyes, indigoid dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes Dyes, phthalimide dyes, perinone dyes and the like can be used. In particular, it is preferable to select a material that absorbs light having wavelengths near the h-line and the i-line, for example, a carbonium-based dye such as basic blue, because the effects of the present invention can be more easily achieved. 0.001-1% by weight of organic dye
It is preferred that

An organic solvent is used to adjust the viscosity when applying the photosensitive paste to the substrate according to the application method. Examples of the organic solvent used at this time include methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, γ-butyl lactone, and bromobenzene. , Chlorobenzene, dibromobenzene, dichlorobenzene,
Bromobenzoic acid, chlorobenzoic acid, and the like, and an organic solvent mixture containing at least one of them are used.

The photosensitive paste is usually made of an ultraviolet absorber,
Antioxidants, inorganic fine particles, photosensitive organic components, organic dyes,
Various components such as a dispersant, a light absorbing agent, and a solvent are blended so as to have a predetermined composition, and then uniformly mixed and dispersed with a three-roller or a kneader to produce.

The viscosity of the paste is appropriately adjusted by the addition ratio of inorganic fine particles, a thickener, an organic solvent, a plasticizer, a suspending agent, etc., but the range is from 2000 to 200,000 cps.
(Centipoise). For example, when the coating on the substrate is performed by the spin coating method, 2000 to 5000 cps
Is preferred. Coated once by screen printing method to obtain a film thickness of 10
In order to obtain ２０20 μm, 50,000 to 200,000 cps is preferable. When using a blade coater method, a die coater method, or the like, 10,000 to 50,000 cps is preferable.

An example in which pattern processing is performed using a photosensitive paste will be described, but the present invention is not limited to this.

On the substrate, the photosensitive paste is applied entirely or partially. As a coating method, a method such as a screen printing method, a bar coater, a roll coater, a die coater, or a blade coater can be used. The coating thickness can be adjusted by selecting the number of coatings, the screen mesh, and the viscosity of the paste.

Here, when applying the paste on the substrate,
Surface treatment of the substrate can be performed to enhance the adhesion between the substrate and the coating film. Examples of the surface treatment liquid include silane coupling agents such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, tris (2-methoxyethoxy) vinylsilane, γ-glycidoxypropyltrimethoxysilane, γ- (methacrylic acid). Roxypropyl) trimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like, or an organic metal such as , Organic titanium,
Organic aluminum, organic zirconium and the like. A silane coupling agent or an organic metal diluted with an organic solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl alcohol, ethyl alcohol, propyl alcohol, or butyl alcohol to a concentration of 0.1 to 5% is used. Used.
Next, this surface treatment liquid is uniformly applied on a substrate by a spinner or the like, and then dried at 80 to 140 ° C. for 10 to 60 minutes to perform surface treatment.

After application, exposure is performed using an exposure device. As an exposure apparatus, a proximity exposure machine or the like can be used. Also, when performing large area exposure,
After applying the photosensitive paste on the substrate, by performing exposure while transporting, with an exposure machine with a small exposure area,
A large area can be exposed.

After exposure, development is carried out using the difference in solubility between the exposed part and the non-exposed part in the developing solution.
It is performed by a dipping method, a spray method, or a brush method. An organic solvent in which an organic component in the photosensitive paste can be dissolved is used as the developer. In addition, water may be added to the organic solvent as long as its solvent power is not lost. When a compound having an acidic group such as a carboxyl group is present in the photosensitive paste, development can be performed with an aqueous alkali solution. As the alkaline aqueous solution, sodium hydroxide, sodium carbonate, calcium hydroxide aqueous solution and the like can be used, but it is preferable to use an organic alkaline aqueous solution since an alkaline component can be easily removed during firing.

As the organic alkali, a general amine compound can be used. Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, diethanolamine and the like.

The concentration of the aqueous alkali solution is usually 0.05 to 5
%, More preferably 0.1 to 1% by weight. If the alkali concentration is too low, the soluble portion is not removed, and if the alkali concentration is too high, the pattern portion may be peeled off and the non-soluble portion may be corroded, which is not good. The development temperature during development is preferably from 20 to 50 ° C. from the viewpoint of process control.

Next, firing is performed in a firing furnace. The firing atmosphere and temperature vary depending on the type of paste or substrate, but firing is performed in an atmosphere such as air, nitrogen, or hydrogen. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used.

The firing temperature is 400 to 1000 ° C. When processing a pattern on a glass substrate, 520 to 610
The firing is carried out at a temperature of 10 ° C. for 10 to 60 minutes.

[0072]

The present invention will be described below in more detail with reference to examples. However, the present invention is not limited to this.

Synthesis Example Synthesis of Compound A (Table 1) Glycidyl methacrylate, 114 g (0.8 mol)
12 g (0.2 mol) of ethylenediamine was added dropwise at room temperature. After the dropwise addition, stirring was continued at 80 ° C., and the disappearance of the raw materials was confirmed using liquid chromatography to obtain Compound A.

Example 1 The photosensitive paste was a polymer (methyl methacrylate / methacrylic acid copolymer, weight composition ratio 50/50, weight average molecular weight 31,000): 1
5 parts by weight, photosensitive monomer (compound A in Table 1): 15 parts by weight, and a photopolymerization initiator (2-benzyl-2)
-Dimethylamino-1- (4-morpholinophenyl)
(Butanone): 4.8 parts by weight, sensitizer (2,4-diethylthioxanthone): 1.2 parts by weight, antioxidant (1,6
-Hexanediol-bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]): 3.
0 parts by weight, an ultraviolet absorber (2-ethylhexyl-2-cyano-3,3-diphenylacrylate, absorption maximum wavelength: 320 nm): 0.5 parts by weight and an organic dye (basic blue 26, absorption maximum wavelength: 592 nm) 0 .0
One part by weight of each component was dissolved while being heated to 50 ° C., and then 70 parts by weight of the following inorganic fine particles were added and kneaded with a kneader. The viscosity was adjusted by the amount of γ-butyrolactone, but the amount of the solvent in the paste was adjusted to 30%. The transmission limit wavelength of the paste at a film thickness of 50 μm was 420 nm, and the wavelength gradient width was 30 nm.

The composition of the inorganic fine particles is Li ₂ O:
_{9%, SiO 2: 22%} , Al 2 O 3: 23%, B 2 O 3:
Glass fine particles of 33%, BaO: 4%, ZnO: 2%, and MgO: 7% were used. The glass particles have an average refractive index of 1.586, a glass transition point and a softening point of 4 respectively.
76 ° C., 519 ° C., the average particle size is 2.6 μm.

A photosensitive paste was uniformly applied on a soda glass substrate by screen printing. Coating and drying were repeated several times or more in order to avoid pinholes or the like on the coating film, and coating was performed so that the dry thickness became 180 μm. Drying was performed at 80 ° C. for 10 minutes. Then, it dried at 80 degreeC for 60 minutes.

Next, exposure was performed through a photomask (striped pattern, pattern pitch 130 μm, line width 20 μm) for forming a partition pattern for a plasma display. At this time, in order to prevent the mask from being contaminated, a gap of 100 μm was provided between the mask and the coating film surface. Thereafter, a 0.3% by weight aqueous solution of monoethanolamine kept at 35 ° C. is developed by spraying with a shower for 180 seconds, and then washed with water using a shower spray to remove a space portion that has not been photocured and glass. A stripe-shaped partition pattern was formed on the substrate.

The partition pattern was observed with a microscope, and the optimum exposure dose at which exfoliation of the exposed portion, meandering of the pattern and burying (remaining film) between the patterns did not occur was examined.

The glass substrate after the processing of the partition pattern was dried at 80 ° C. for 15 minutes, and then baked at 560 ° C. for 15 minutes to form a partition. The firing causes a shrinkage of about 30%.

(Examples 2 to 6 and Comparative Examples 1 to 4) A partition pattern was formed in the same manner as in Example 1 except that the photosensitive monomers were changed as shown in Table 2, and observed with a microscope. The optimum exposure amount at which the exposed portion did not peel off, meandering of the pattern, and burying between the patterns (remaining film) did not occur, is shown in Table 2.

[0081]

[Table 2]

(Embodiment 7) A pitch of 375 μm was formed on six glass substrates PD200 manufactured by Asahi Glass Company using ITO.
A scan electrode having a line width of 150 μm was formed. Further, after applying a photosensitive silver paste on each substrate, a mask exposure through a photomask, a development using a 0.3% sodium carbonate aqueous solution, a baking process at 580 ° C. for 15 minutes, and a line width of 50 μm were performed. A bus electrode having a thickness of 3 μm was formed.

Next, a glass paste obtained by kneading 70% of a low-melting glass powder containing 75% by weight of lead oxide, 20% of ethylcellulose, and 10% of terpineol was screen-printed on each substrate. The coating was applied at a thickness of 50 μm so as to cover the bus electrode in the display portion, and then baked at 570 ° C. for 15 minutes to form a front dielectric layer.

A 0.5 μm thick protective film was formed on each of the substrates on which the front dielectric layer was formed by electron beam evaporation.
To form six front plates.

Next, a photosensitive silver paste was applied on another six PDs 200, and dried, exposed, developed, and fired to form address electrodes having a line width of 50 μm, a thickness of 3 μm, and a pitch of 250 μm.

Next, 60% of powder of low melting point glass containing 75% by weight of bismuth oxide, 10% by weight of titanium oxide powder having an average particle diameter of 0.3 μm, and 15% of ethyl cellulose
% And terpineol 15% are kneaded and applied to each substrate by screen printing to a thickness of 50 μm so as to cover the address electrodes, and then baked at 570 ° C. for 15 minutes to obtain a dielectric material. A body layer was formed.

Using the photosensitive paste used in Examples 1 to 6, partitions were formed on the dielectric layer of each substrate by photolithography. After drying the photosensitive paste using a die coater to a thickness of 180 μm, the photosensitive paste is exposed using a photomask having an opening line width of 30 μm, and then developed in a 0.5% by weight ethanolamine aqueous solution. Further, by baking at 560 ° C. for 15 minutes, the pitch is about 250 μm, the line width is about 30 μm, and the height is about 130 μm.
A partition of about μm was formed.

Next, a phosphor was applied between adjacent partition walls. The phosphor was applied in 256 holes (130 μm in diameter).
m) was formed by a dispenser method in which a phosphor paste was discharged from the tip of the nozzle formed. The phosphor has a thickness of 25 μm after firing on the side wall of the partition and a thickness of 25 μm after firing on the dielectric.
m, and baked at 500 ° C. for 10 minutes.

Further, the produced front substrate and rear substrate were sealed using sealing glass, and a Ne gas containing 5% of Xe was sealed so as to have an internal gas pressure of 66500 Pa. Further, six sets of plasma displays were manufactured by mounting a drive circuit. A voltage was applied to the scan electrode of the plasma display to emit light. When the luminance was measured using the luminance meter, all the plasma displays were 250c.
d / m ² or more, a good display state.

[0090]

The photosensitive paste of the present invention has high sensitivity, and can process a thick film with a low exposure amount in a short time. Processing becomes possible, and fineness can be improved and the process can be simplified. In particular, partition walls of a plasma display panel can be formed at low cost.

Claims (13)

[Claims] 1. A photosensitive paste containing inorganic fine particles and a photosensitive organic component as essential components, wherein the photosensitive organic component contains a compound represented by the following general formula (I). (I) R ¹ R ³ NL-NR ² R ^{4 wherein} R ¹ and R ² are a substituent having an ethylenically unsaturated group, and R ³ and R ⁴ are an ethylenically unsaturated group , A hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, and an aralkyl group, which may be the same or different. L represents a divalent linking group. ] 2. In the above formula (I), R ¹ , R ² , R
³ and R ⁴ are all CH ₂ = CCH ₃ COOCH ₂ CHOCHCH ₂
The photosensitive paste according to claim 1, which is: 3. The photosensitive paste according to claim 1, wherein the compound represented by the general formula (I) is contained in the photosensitive organic component in an amount of 10 to 80% by weight. 4. The photosensitive paste according to claim 1, further comprising a compound selected from a benzophenone compound, a cyanoacrylate compound, a benzotriazole compound and an indole compound as an ultraviolet absorber. 5. The photosensitive paste according to claim 1, wherein a transmission limit wavelength of the photosensitive paste film at a film thickness of 50 μm is 400 nm or more. 6. The photosensitive paste according to claim 5, wherein the wavelength gradient width of the photosensitive paste film at a film thickness of 50 μm is 50 nm or less. 7. An antioxidant is added to the paste in an amount of 0.01 to 30.
The photosensitive paste according to any one of claims 1 to 6, which contains 0.1% by weight. 8. An inorganic fine particle having an average refractive index of from 1.5 to 1.5.
A glass powder in the range of 1.65 is used.
A photosensitive paste according to any one of the above. 9. At least one of lithium oxide, sodium oxide, and potassium oxide as inorganic fine particles is 3-1.
9. The photosensitive paste according to claim 1, wherein a glass powder containing 0% by weight is used. 10. The glass powder is expressed in terms of oxide as lithium oxide: 3 to 10% by weight Silicon oxide: 10 to 30% by weight Boron oxide: 20 to 40% by weight Barium oxide: 2 to 15% by weight Aluminum oxide: 10 to 10% The photosensitive paste according to claim 8, comprising 25% by weight. 11. A glass powder having a glass transition point of 430-5.
The temperature of 00 ° C and the softening point of 470-580 ° C.
0. The photosensitive paste according to any one of the above. 12. A method of manufacturing a plasma display, comprising a step of forming a pattern by photolithography after applying a photosensitive paste on a substrate and drying, and baking the pattern to form a partition. A method for manufacturing a plasma display, comprising using the photosensitive paste according to claim 1 as the conductive paste. 13. A member for a plasma display manufactured using the photosensitive paste according to claim 1. Description: