JP2000090738A - Photosensitive glass paste composition and burned material pattern formation method using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a highly fine burned material pattern which is excellent in viscosity stability and shows a high resolution characteristic. SOLUTION: This composition contains a polymer (A) whose average molecular weight is 1,000-50,000 and which has two groups or more shown in a formula at a side chain, a photo-polymerization initiator (B), a compound (C) which generates an acid by heating, a photo-polymerization monomer (D), a dilution solvent (E), a glass frit (F), and moreover inorganic powder (G) such as ceramic powder, black pigment or conductive metal powder. A substrate is coated with the composition, which is heated and dried to form a tack free coating film and to generate an acid simultaneously. Then, a side chain of the polymer (A) is deblocked to generate a carboxylic acid. Thereafter, an active energy is selectively applied, while a coating film at a non-irradiated part is developed with an alkali solution, and removed. Finally, a baking process is applied. In the formula, R1 shows a hydrogen atom and R2 shows a group substituted by an alkyl group whose carbon numbers are 1-18 or an alkoxyl group whose carbon numbers are 1-6, and R1 and R2 may be combined with each other to form a composite ring.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkali-developable and negative photosensitive glass paste composition and a partition wall pattern, a conductive circuit pattern, a black matrix pattern and the like of a plasma display panel (PDP) using the same. The present invention relates to a method for forming a fired product pattern such as a dielectric pattern.

[0002]

2. Description of the Related Art A PDP is a flat panel display for displaying images and information by utilizing light emission by plasma discharge.
It is classified into DC type and AC type according to the panel structure and driving method. The principle of color display by PDP is rib (partition)
A plasma discharge is generated in a cell space (discharge space) between the opposed electrodes formed on the front glass substrate and the rear glass substrate which are separated from each other by gas, and a gas such as He or Xe sealed in each cell space. The phosphor formed on the inner surface of the rear glass substrate is excited by ultraviolet rays generated by the discharge of the liquid crystal to generate visible light of three primary colors. Each cell space is D
C-type PDPs are defined by lattice-shaped ribs, while AC-type PDPs are defined by ribs arranged in parallel to the substrate surface. In any case, the cell space is defined by ribs. .

FIG. 1 shows an example of the structure of a surface discharge type PDP having a three-electrode structure for full color display. On the lower surface of the front glass substrate 1, a pair of display electrodes 2a and 2b each including a transparent electrode 3a or 3b for discharging and a bus electrode 4a or 4b for lowering the line resistance of the transparent electrode are formed. On these display electrodes 2a and 2b, a transparent dielectric layer 5 (low-melting glass) for storing electric charges is printed,
The protective layer (MgO) 6 is formed by baking. The protective layer 6 has a role of protecting a display electrode, maintaining a discharge state, and the like.

On the other hand, on the back glass substrate 11, stripe-shaped ribs (partitions) 12 for dividing a discharge space and address electrodes (data electrodes) 13 arranged in each discharge space are formed at a predetermined pitch. ing. On the inner surface of each discharge space, phosphor films of three colors of red (14a), blue (14b), and green (14c) are regularly arranged. In the full-color display, one pixel is formed by the phosphor films of the three primary colors of red, blue, and green as described above. In the PDP, an AC pulse voltage is applied between a pair of display electrodes 2a and 2b to cause a discharge between the electrodes on the same substrate, and is called a "surface discharge method". The ultraviolet light generated by the discharge excites the phosphor films 14a, 14b, 14c of the rear substrate 11, and the generated visible light is transmitted to the transparent electrodes 3a, 3a of the front substrate 1.
b (reflection type).

Heretofore, in forming a partition of a plasma display panel, patterning by a screen printing method using a glass paste has been generally performed. But,
Pattern formation by the screen printing method requires skill, and there are problems such as rubbing and bleeding during printing, a decrease in alignment accuracy due to expansion and contraction of the screen, a low yield, a large screen of the plasma display panel and It has become difficult to respond to high definition.

Therefore, a photolithography method has been proposed as a rib forming method that can replace the screen printing method (for example, Japanese Patent Application Laid-Open Nos. 1-296534 and 2).
165538, JP-A-5-342992).
In the photolithography method, a substrate is coated with a UV-curable glass paste material, and a pattern is formed by exposure and development. Further, it has been proposed to add a black pigment to the glass paste in order to prevent halation at the time of ultraviolet curing (see JP-A-6-144871). In order to make the alkali development type useful means as a photolithography method, a polymer compound having both a carboxyl group and an unsaturated double bond, or a polymer having these functional groups separately,
It is generally known that a monomer or the like is added to a glass paste together with a photopolymerization initiator to form a negative photosensitive composition.

[0007]

However, as a problem of the negative photosensitive glass paste, there is a problem of viscosity stability that when a basic glass powder and a polymer compound having a carboxyl group are mixed, the viscosity increases in a short time. There is. Therefore, JP-A-9-222723 proposes adding an organic acid to prevent thickening, and JP-A-9-218509 proposes adding phosphoric acid. However, in each case, since an acidic component is added to the glass paste in addition to the polymer compound having a carboxyl group, there is a problem that the development resistance of the photocured portion is reduced during alkali development. Further, since the surface of the basic glass fine particles and the acidic component react with time, there is a problem that the resolution is hardly stabilized.

The present invention has been made in view of the above-mentioned problems of the prior art, and its basic purpose is to provide a storage stability (viscosity) even when an extremely large amount of glass frit or inorganic fine powder is contained. Stability), high resolution, and the photo-cured part has excellent development resistance during alkali development, and can be used to form a high-definition, high-aspect-ratio fired product pattern. An object of the present invention is to provide a functional glass paste composition. Another object of the present invention is to form a high-definition partition pattern, a conductive circuit pattern, and a fired product pattern such as a dielectric pattern from a photosensitive glass paste composition as described above by photolithography technology with good workability and productivity. It is to provide a method that can be performed.

[0009]

In order to achieve the above object, according to a first aspect of the present invention, there is provided an alkali-developable photosensitive glass paste composition. A) a group represented by the following general formula (1)
Weight average molecular weight of 1,000 to 50,000
(B) a compound that generates a radical upon irradiation with active energy rays, (C) a compound that generates an acid upon heating, (D) a photopolymerizable monomer, (E) a diluting solvent, and (F) a glass frit It is characterized by containing.

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The second aspect is that (A) a polymer having a weight average molecular weight of 1,000 to 50,000 having two or more groups represented by the general formula (1) in the side chain; Compounds that generate radicals upon irradiation with energy rays,
(C) a compound that generates an acid upon heating, (D) a photopolymerizable monomer, (E) a diluting solvent, (F) a glass frit, and (G) an inorganic powder other than the glass frit. Alkali-developable photosensitive glass paste composition. The inorganic powder (G) contains at least one of ceramic powder, black pigment, and conductive metal powder.

Further, according to a second aspect of the present invention, there is provided a method for forming a fired product pattern, the first method comprising:
Applying the photosensitive glass paste composition to a substrate, heating and drying the applied layer to form a tack-free coating film, and simultaneously generating an acid to deblock the side chain of the polymer (A). Developing a carboxylic acid, selectively irradiating the coating film with an active energy ray, developing and removing the coating film of the non-irradiated portion with an alkaline aqueous solution, and baking the developed pattern. It is characterized by including.

On the other hand, a second method comprises a step of applying the photosensitive glass paste composition to a substrate, a step of heating and drying the applied layer to form a tack-free coating, and a step of applying an active energy ray to the coating. Selectively irradiating, heating the coating film after the irradiation, deblocking the side chain of the polymer (A) to express carboxylic acid, and developing the coating film of the non-irradiated portion with an aqueous alkali solution. And baking the developed pattern. The fired product pattern formed in this manner is, in addition to the partition pattern and the dielectric pattern of the plasma display panel,
When a conductive metal powder is used as the inorganic powder (G), a conductive pattern is formed.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive glass paste composition according to the present invention is prepared by preliminarily blocking a carboxyl group of an alkali-soluble polycarboxylic acid resin, so as to react with a basic glass component and to increase the viscosity of the reaction. It prevents the rise and develops the carboxyl group by causing deblocking by heating after applying the paste, which makes it possible to easily form a large-area high-definition fired product pattern by photolithography technology. It was done. That is, the photosensitive glass paste composition according to the present invention comprises a polymer (A) having two or more groups represented by the general formula (1) in a side chain as a film-forming component and a photopolymerizable monomer (D). In combination with a compound that generates radicals upon irradiation with active energy rays (hereinafter referred to as a photopolymerization initiator) (B) and a compound that generates an acid upon heating (hereinafter referred to as a thermal acid generator) (C). It is characterized by:

First, in the first method, after applying the photosensitive glass paste composition on a substrate, the organic solvent is volatilized by drying by heating to, for example, 50 ° C. or more.
A tack-free coating is formed and contact exposure is possible. At this time, although it depends on the thermal acid generator used, for example, 8
When heated above 0 ° C., the thermal acid generator (C) thermally decomposes to generate an acid. By the catalytic action of this acid, deblocking of the side chain of the polymer (A) occurs, and carboxylic acid is expressed. For example, when the polymer (A) is obtained by blocking a carboxyl group of a polycarboxylic acid resin with a monovinyl ether compound, the polycarboxylic acid is catalyzed by an acid generated by thermal decomposition of the thermal acid generator (C), and the polycarboxylic acid is catalyzed. Decomposes into acid resin and monovinyl ether compound. Since the polycarboxylic acid resin has a free carboxyl group in a side chain, it is soluble in a weak alkaline aqueous solution and becomes a component that is dissolved in a subsequent development step.

Thereafter, when the active energy ray is selectively irradiated through a photomask on which a predetermined exposure pattern is formed, the photopolymerization initiator (B) causes the photopolymerizable monomer (D) existing in the coating film of the irradiated portion to be irradiated. Radical polymerization occurs, and the coating film in the irradiated part is cured, and becomes a coating resistant to a weak alkaline aqueous solution. Therefore, after that, when developing with a weak alkaline aqueous solution, only the coating film in the non-irradiated portion is dissolved and removed. Next, by performing firing, the organic components are burned off, and a predetermined fired product pattern is formed.

On the other hand, the second method is such that the acid generation by the thermal decomposition of the thermal acid generator (C) and the accompanying carboxylic acid expression of the polymer (A) occur before the development step. It is. In this case, heating after application is stopped to a degree of drying for forming a tack-free coating film, and after the step of selectively irradiating active energy rays, generation of acid by thermal decomposition of thermal acid generator (C) and polymer What is necessary is just to implement the heating process of the conditions (A) which can produce the carboxylic acid expression. In addition,
Also in the first method described above, when the carboxylic acid expression of the polymer (A) is insufficient by the heat treatment after the application, the heating step after the irradiation with the active energy ray can be further performed.

As described above, since the carboxyl group in the side chain of the polymer (A) used in the photosensitive glass paste composition of the present invention is previously blocked as shown by the general formula (1), Will not react with powder. Therefore, the viscosity of the glass paste composition does not increase, and the glass paste composition has excellent viscosity stability. Further, the carboxylic acid of the polymer (A) is rapidly expressed by the catalytic action of the acid generated by the thermal decomposition of the thermal acid generator (C), so that stable resolution is exhibited. Moreover, since the polymer itself does not contain a double bond, the curing shrinkage during subsequent baking is significantly reduced as compared with the case where a photosensitive resin is used as in a conventional negative-type photosensitive glass paste composition. And a high definition fired product pattern can be formed. Further, the yield rate is greatly improved because the defective rate of the formed fired product pattern is extremely reduced.

The composition of the present invention is basically composed of the following components. (A) a polymer having a weight average molecular weight of 1,000 to 50,000 having two or more groups represented by the general formula (1) in a side chain, (B) a photopolymerization initiator, and (C) a thermal acid generator , (D)
A photopolymerizable monomer, (E) a diluting solvent, (F) a glass frit, or (G) a ceramic powder (G-
1) Inorganic powders such as black pigment (G-2) and conductive metal powder (G-3). A preferable composition ratio is such that the polymer (A) 10
2 to 40 parts by weight of the photopolymerization initiator (B), 2 to 40 parts by weight of the thermal acid generator (C), 2 to 100 parts by weight of the photopolymerizable monomer (D), and glass frit per 0 parts by weight. (F) is 10 to 1,000 parts by weight, and the diluting solvent (E) can be blended in any ratio depending on the desired viscosity at the time of paste application. When adding ceramic powder (G-1) or black pigment (G-2), use glass frit (F)
Ceramic powder (G-1) is 1 to 100 parts by weight
100 parts by weight and the range of 3 to 50 parts by weight of the black pigment (G-2) are preferred. These are (A), (B), (C),
(E), (F), (G-1),
It is preferable to mix the components (G-2) so that the total sum of the components is 0.5 to 50 times. In addition to these components, acrylic and silicone defoaming and leveling agents can be added as needed. On the other hand, in order to impart conductivity, Ag, Au, Pd, Ni,
By using a conductive metal powder (G-3) such as Cu, Al, or Pt, a conductive paste can be obtained. In this case, the amount of the conductive metal powder (G-3) to be added is (A), (B), (C), (D), (E), (F),
The composition comprising (G-1) and (G-2) having the above composition ratio can be arbitrarily selected in an amount sufficient to impart conductivity.

The polymer (A) used in the present invention is a polymer having a polymerization average molecular weight of 1,000 to 50,000 having two or more groups represented by the general formula (1) in the side chain.
In a preferred embodiment, the solid content acid value is 60 to 300 mgK.
There is a resin obtained by adding a monovinyl ether compound to an OH / g polycarboxylic acid resin. When the weight average molecular weight of the polymer is less than 1,000, the strength of the dried coating film is lost, and the coating film is easily peeled off during development, which is not preferable. On the other hand, when the weight average molecular weight exceeds 50,000, development with a weak alkaline aqueous solution becomes difficult, which is not preferable. Further, when the acid value of the polycarboxylic acid resin as the starting material is less than 60 mgKOH / g, the acid value of the polycarboxylic acid resin decomposed and generated from the polymer by heating is low, and thus the coating film is not irradiated with active energy rays. On the other hand, it is difficult to develop a portion with a weak alkaline aqueous solution, while if the acid value exceeds 300 mgKOH / g, it is difficult to obtain the development resistance of the active energy ray irradiated portion of the coating film, which is not preferable.

The polycarboxylic acid resin is a film-forming polymer having at least two carboxyl groups in one molecule. For example, (meth) acrylic acid (acrylic acid, methacrylic acid, and a mixture thereof are collectively referred to as (meth) acrylic acid). The same applies to (meth) acrylate described later), a homopolymer of a polymerizable unsaturated monomer such as crotonic acid and itaconic acid, and a copolymer of the carboxyl group-containing monomer and another copolymer. Copolymers with polymerizable monomers, resins obtained by adding acid anhydrides to polyols such as polyvinyl alcohol, polyesters having a carboxyl group in the molecular chain and / or at the molecular terminal, polyurethanes, polyamides, etc. Although a resin etc. are mentioned, Among these, the copolymer resin containing 8-40 weight% of (meth) acrylic acid is preferable. Styrene, chlorostyrene, α-
Unsubstituted or substituted styrene such as methylstyrene; as a substituent, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, amyl, 2-ethylhexyl, octyl, capryl, nonyl, dodecyl, hexadecyl, octadecyl, cyclohexyl , Alkyls such as isobornyl, alkoxyalkyls such as methoxyethyl and butoxyethyl, 2-hydroxyethyl, 2-
Acrylate, methacrylate or fumarate having a substituent such as hydroxyalkyl such as hydroxypropyl and 3-chloro-2-hydroxypropyl; monoacrylate or monomethacrylate of polyalkylene glycol such as polyethylene glycol and polypropylene glycol; vinyl acetate, vinyl butyrate And vinyl esters such as vinyl benzoate; olefins such as ethylene and propylene; and acrylonitrile. These can be used alone or as a mixture of two or more. However, it is more preferable to use (meth) acrylates not containing a benzene ring from the viewpoint of burnout. When the content of (meth) acrylic acid in the polycarboxylic acid resin is less than 8% by weight, the acid value of the obtained copolymer resin becomes small, and the non-irradiated portion of the coating film with the active energy ray is developed with a weak alkaline aqueous solution. It is not preferable because it becomes difficult to perform. on the other hand,
If the content of (meth) acrylic acid exceeds 40% by weight, it is difficult to control the amount of the monovinyl ether compound to obtain sufficient development resistance of the coating film, which is not preferable.

Examples of the monovinyl ether compound which is one of the reaction compounds to be added to the polycarboxylic acid resin include vinyl methyl ether, vinyl ethyl ether, vinyl isopropyl ether, vinyl-n-propyl ether, vinyl isobutyl ether, vinyl-n -Butyl ether, vinyl-t-butyl ether, vinyl-n-
Amyl ether, vinyl isoamyl ether, vinyl-
Examples include n-octadecyl ether, ethylene glycol butyl vinyl ether, triethylene glycol monomethyl vinyl ether, and the like, and also include cyclic vinyl ethers such as 3,4-dihydro-2H-pyran. Among these, a monovinyl ether compound having a boiling point of 30 to 200 ° C is preferable. When the boiling point of the monovinyl ether compound is lower than 30 ° C., it is difficult to add the monovinyl ether compound to the polycarboxylic acid resin during the synthesis of the polymer (A). On the other hand, when the boiling point exceeds 200 ° C., during the heat treatment of the coating film, a reversible reaction occurs in which the monovinyl ether compound produced by the thermal decomposition of the polymer (A) is re-added to the polycarboxylic acid resin produced at the same time, It is not preferable because the non-irradiated part of the coating film with the active energy ray becomes difficult to develop with a weak alkaline aqueous solution.

These monovinyl ether compounds are reacted with a polycarboxylic acid resin in a suitable catalyst at room temperature to 100 ° C. to produce the polymer (A). Although this synthesis reaction proceeds even in the absence of a catalyst, a small amount of an acid catalyst, a layer transfer catalyst, or the like can be used as necessary. The addition rate of the monovinyl ether compound to the carboxyl group of the polycarboxylic acid resin is preferably 50% or more. Addition rate is 50%
If the ratio is less than 10%, development resistance of a portion of the coating film irradiated with active energy rays to a weak alkaline aqueous solution becomes insufficient, and it becomes difficult to form a good pattern, which is not preferable. Furthermore, since the free carboxylic acid serves as a decomposition catalyst at the time of heating or inhibits the stability of the glass paste, it is preferable to increase the addition rate of the monovinyl ether compound to 90% or more.

The photopolymerization initiator (B) used in the present invention includes benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenyl Acetophenones such as acetophenone, 2,2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, Α-aminoalkylphenones such as -benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, -Chloroanthraquinone Anthraquinones such as 2-amyl anthraquinone; 2,4-dimethyl thioxanthone, 2,
Thioxanthones such as 4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone;
Benzophenones such as 4-benzoyl-4'-methyldiphenylsulfide; acylphosphines such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; visible region shown in JP-A-10-81838. Onium borate complexes such as a combination of a cationic dye having an absorption in water and a quaternary boron sensitizer; bis (η5-2,4-cyclopentadiene-1-
Metallocene compounds such as yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium. These known and commonly used photopolymerization initiators can be used alone or in combination of two or more. These photopolymerization initiators (B) are N, N
-Dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-
4-dimethylaminobenzoate, triethylamine,
It can be used in combination with one or more commonly known photosensitizers such as tertiary amines such as triethanolamine.

The thermal acid generator (C) used in the present invention includes α-phenylbenzyl-4-cyanopyridium hexafluoroantimonate, α-phenylbenzyl-
2-vinylpyridium hexafluoroantimonate, α
-Phenylbenzyl-2- (4-chlorobenzyl) pyridium hexafluoroantimonate, α-phenylbenzyl-4-benzoylpyridium hexafluoroantimonate, α-phenylbenzyl-4-cyanopyridium hexafluorophosphate, α -Phenylbenzyl-
4-cyanopyridium tetrafluoroborate, benzyl-4-cyanopyridium hexafluoroantimonate,
1- (4-methoxybenzyl) -4-cyanopyridium hexafluoroantimonate, 1- (4-methylbenzyl) -4-cyanopyridium hexafluoroantimonate, 1- (4-methylbenzyl) -2-chloro Pyridinium salts such as pyridium tetrafluorophosphate;
Benzyltetramethylenesulfonium hexafluoroantimonate, benzyltetramethylenesulfonium hexafluorophosphate, p-methoxybenzyltetramethylenesulfonium hexafluoroantimonate, p
-Methoxybenzyltetramethylenesulfonium hexafluorophosphate, 1-naphthylmethyltetramethylenesulfonium hexafluorophosphate, 1-naphthylmethyltetramethylenesulfonium hexafluoroantimonate, p-acetylbenzyltetramethylenesulfonium hexafluoroantimonate, p-carboxy -4-hydroxybenzyltetramethylenesulfonium hexafluoroantimonate, o-sulfonylbenzyltetramethylenesulfonium hexafluoroantimonate, α-phenylbenzyldimethylsulfonium hexafluoroantimonate, α-phenylbenzyltetramethylenesulfonium hexafluoroantimonate,
sulfonium salts such as α-phenylbenzyldiethylsulfonium hexafluoroantimonate; N- (methylbenzyl) -N, N-dimethylanilium-p-dodecylbenzenesulfonate; N- (α, α-dimethylbenzyl) -4-chloro Sulfonates such as pyridium-p-dodecylbenzenesulfonate; p-toluenesulfonic acid (1-methylethyl), p-toluenesulfonic acid (cyclohexyl), p-toluenesulfonic acid (1-propylbutyl), p-toluene And sulfonic acid esters such as sulfonic acid (1-propyloctyl).

In the present invention, the photopolymerizable monomer (D) is used for imparting photocurability to the composition and for improving developability. Examples of the photopolymerizable monomer (D) include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polyurethane diacrylate, trimethylolpropane triacrylate, and pentaerythritol triacrylate. Acrylate, pentaerythritol tetraacrylate, trimethylolpropane ethylene oxide modified triacrylate, trimethylolpropane propylene oxide modified triacrylate, dipentaerythritol pentaacrylate,
Dipentaerythritol hexaacrylate and each methacrylate corresponding to the above acrylate, mono- of polybasic acid and hydroxyalkyl (meth) acrylate,
Examples thereof include di-, tri-, and more polyesters, and these can be used alone or in combination of two or more.

The diluting solvent (E) used in the present invention can be added to the composition to adjust the viscosity, impart fluidity, facilitate the coating process, and then dry to form a film, which enables contact exposure. It is used for Specifically, ketones such as methyl ethyl ketone and cyclohexanone;
Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene Glycol ethers such as ethylene glycol monoethyl ether; ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, acetate esters such as propylene glycol monomethyl ether acetate; ethanol, propanol, ethylene glycol, Alcohols such as propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum Ether, petroleum naphtha, hydrogenated petroleum naphtha, include petroleum solvents such as solvent naphtha, may be used alone or in combination of two or more of these solvents.

The glass frit (F) used in the photosensitive glass paste composition of the present invention has a softening point of 300 to 300.
A low melting glass frit of 600 ° C. is used, and lead oxide,
Those containing bismuth oxide or zinc oxide as a main component can be suitably used. In addition, as a low melting point glass frit,
A glass transition temperature of 300 to 550 ° C., the thermal expansion coefficient alpha _{30 0}
= 70 to 90 × 10 ⁻⁷ / ° C. It is preferable to use those having an average particle diameter of 20 μm or less, preferably 5 μm or less from the viewpoint of resolution.

Preferable examples of the glass powder containing lead oxide as a main component are as follows.
82%, B ₂ 0 ₃ is 0.5 to 22%, SiO ₂ is 3 to 32
%, Al ₂ O ₃ is 0 to 12%, BaO is 0%, Zn
O is 0 to 15% TiO ₂ is 0 to 2.5% Bi ₂ O ₃ has a composition of 0% to 25%, softening point include noncrystalline frit is four hundred and twenty to five hundred ninety ° C..

As a preferred example of the glass powder containing bismuth oxide as a main component, Bi ₂ O ₃
There 35~88%, B ₂ O ₃ is 5 to 30%, SiO ₂ is 0
20%, Al ₂ O ₃ is 0 to 5%, BaO is 1 to 25%, Z
nO has a composition of 1 to 20% and a softening point of 420 to 59.
A non-crystalline frit at 0 ° C.

As a preferred example of the glass powder containing zinc oxide as a main component, ZnO is 25% by weight on an oxide basis.
６０60%, K ₂ O 2-15%, B ₂ O ₃ 25-45
%, SiO ₂ is 1~7%, Al ₂ O ₃ is 0%, Ba
An amorphous frit having a composition of 0 to 20% of O and 0 to 10% of MgO and having a softening point of 420 to 590 ° C is exemplified.

In the photosensitive glass paste composition of the present invention, a glass frit (F) is used for stabilizing the shape after firing.
1 to 100 parts by weight of ceramic powder (G-1) can be added per 100 parts by weight. Examples of the ceramic powder include alumina, titanium oxide, magnesium oxide, barium oxide, zinc oxide, calcium oxide, and the like, and they can be used alone or in combination of two or more. These ceramic powders have an average particle size of 20 μm in terms of resolution.
m or less, preferably 5 μm or less.

In the composition of the present invention, 3 to 100 parts by weight of the glass frit (F) is used to improve the blackness after firing.
50 parts by weight of a black pigment (G-2) can be added. As the black pigment, a metal oxide black pigment containing two or more kinds of oxides such as Cu, Fe, Cr, Mn, and Co as main components can be suitably used.
_{Cr 2 O 3, CuO-Fe} 2 O 3 -Mn 2 O 3, CuO-Fe
₂ O ₃ —Cr ₂ O _{3 and the} like. The average particle size of the black pigment is 20 μm or less, preferably 5
The one having a size of μm or less is used. On the other hand, in terms of blackness, those having an average particle size of 1.0 μm or less, preferably 0.6 μm or less are suitable.

Since the inorganic powder used in the present invention preferably has a particle size of 10 μm or less, the properties of the inorganic powder are impaired for the purpose of preventing secondary aggregation and improving dispersibility. As far as the composition is not known, it is possible to use a material which has been surface-treated in advance with a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, or the like, or to add the above-mentioned treating agent when the composition is pasted.

When the photosensitive glass paste composition of the present invention is formulated as a conductive paste, silver is used as an inorganic powder.
Conductive metal powder (G-3) such as gold, copper, palladium, platinum, aluminum, nickel or the like, or an alloy thereof and / or inorganic fine particles such as glass particles coated with these can be used. These conductive metal powders may be used alone or
More than one kind can be used in combination, and the average particle size is 10 μm or less, preferably 5 μm in terms of resolution.
The following particle sizes are preferred. In addition, these metal fine particles can be used alone or in combination of two or more in the form of a sphere, a block, a flake, or a dendrite. Further, in order to prevent oxidation of these metal fine particles, improve dispersibility in the composition, and stabilize developability, in particular, Ag,
Ni and Al are preferably treated with fatty acids. Fatty acids include oleic acid, linoleic acid, linolenic acid, stearic acid and the like. When a two-layer conductive circuit pattern of a black lower layer and a white upper layer is formed to increase the contrast, a conductive metal powder and a black pigment are used in combination for the glass paste composition for forming the lower layer.

The amount of the conductive metal powder (G-3) is from 25 to 1,000 parts by weight per 100 parts by weight of the total of the components (A), (B), (C) and (D). The ratio is appropriate. If the amount of the metal powder is less than the above range, the line width of the conductor circuit is likely to shrink or break, whereas if the amount is more than the above range, light transmission is impaired and sufficient resolution is obtained. It is difficult to obtain. Further, in order to improve the strength of the film after firing and the adhesion to the substrate, the above glass frit (F) is added in the range of 5 to 30 parts by weight per 100 parts by weight of the conductive metal powder (G-3). Is preferred.

The photosensitive glass paste composition of the present invention comprises:
As far as the desired properties are not impaired, and further, if necessary, a known and commonly used antioxidant for preventing the oxidation of the conductive metal powder, or a thermal polymerization ban for improving the thermal stability during storage. Agents, fine particles such as metal oxides, silicate oxides, and boron oxides as binding components with the substrate during firing, and defoaming and leveling agents for smoothing the coating film and improving foam disappearance after printing Can also be added.

When forming a partition pattern, a conductor circuit pattern and the like of a plasma display panel using the glass paste composition of the present invention, the glass paste composition is applied to a plasma display panel by a screen printing method, a bar coater, a blade coater or the like. Apply on a glass substrate. Next, the diluting solvent is evaporated at 50 ° C. or more in a hot air circulation type drying furnace or the like in order to obtain dryness to the touch. At that time, in order to thermally decompose the thermal acid generator (C), the heating temperature should be 80.
C or higher is desirable. At this time, the group that had blocked the carboxyl group of the polymer (A) was deblocked by the catalytic action of the acid generated from the thermal acid generator (C) by heating, and came off. Is done. Thereafter, selective exposure, development, and firing are performed to form a predetermined fired product pattern.

As the exposure step, contact exposure and non-contact exposure using a photomask having a predetermined exposure pattern are possible, but contact exposure is preferred from the viewpoint of resolution.
The exposure environment is preferably in a vacuum or under a nitrogen atmosphere. As an exposure light source, a halogen lamp, a high-pressure mercury lamp, a laser beam, a metal halide lamp, a black lamp, an electrodeless lamp, or the like is used.

Further, after the exposure, reheating may be performed to cause or further accelerate the decomposition reaction of the thermal acid generator (C). The heating step at this time is about 60 to 150 ° C.
For 5 to 60 minutes, preferably at 80 to 120 ° C for 5 to 30 minutes. This step can be replaced by a drying step.

As the developing step, a spray method or an immersion method is used. As the developing solution, an aqueous solution of an alkali metal such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium silicate, or an aqueous solution of an amine such as monoethanolamine, diethanolamine or triethanolamine is preferably used. Coalescing (A)
It is sufficient that the carboxyl group of the polycarboxylic acid resin in the composition formed by thermal decomposition is saponified and the non-exposed portion is removed, and is not limited to the developer described above. Further, it is preferable to perform washing with water or acid neutralization to remove an unnecessary developer after the development.

Subsequently, as a firing step, the substrate after development is subjected to a heat treatment at about 380 to 600 ° C. in air or in a nitrogen atmosphere to form a fired product pattern. At this time, it is preferable to include a step of heating to about 300 to 500 ° C. and maintaining the temperature at that temperature for a predetermined time to remove organic substances as a step before the firing step.

[0042]

EXAMPLES The present invention will be described in detail with reference to the following examples, but it goes without saying that the present invention is not limited to the following examples. "Part" and "%"
All parts are by weight unless otherwise specified.

Example of Resin Synthesis In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, 362.7 parts of dipropylene glycol monomethyl ether and 11.5 parts of azobisisobutyronitrile were added.
And heated to 75 ° C. Thereto, a mixed solution of 72.0 parts of acrylic acid, 330 parts of methyl methacrylate, and 65.5 parts of 2-hydroxyethyl methacrylate was dropped over 3 hours. Thereafter, the mixture was further stirred for 4 hours to obtain a resin solution. The obtained copolymer resin had a weight average molecular weight of 21,000 and an acid value of 118 mgKOH / g. After cooling the resin solution to room temperature, 150 parts of vinyl isobutyl ether was added and reacted at 50 ° C. for 48 hours to confirm that vinyl isobutyl ether was added to 95% of the carboxyl groups of the resin by measuring the acid value. did. Unreacted vinyl isobutyl ether remaining in the reaction solution was removed by an evaporator to obtain a resin solution. This resin solution is called A varnish.

Examples 1 to 5 Using the A varnish obtained in the above resin synthesis example, compounding it in the composition ratio shown in Table 1, stirring with a stirrer, kneading with a three-roll mill, and forming a paste. Was done. The glass frit used at this time had an average particle size of 2.5 μm. As the black pigment, heat-resistant black # 3900 manufactured by Asahi Kasei Kogyo Co., Ltd. having an average particle size of 1 μm was used.

Substrate preparation method 1: Evaluation substrates were prepared for the respective glass paste compositions prepared in Examples 1 to 4 under the following conditions. 300 whole surface on one side of the glass substrate
The composition one hour after the preparation is applied using a mesh polyester screen. Next, it is dried at 100 ° C. for 30 minutes using a hot air circulation type drying furnace. Next, using a negative film of a grid pattern having a line width of 50 μm, a metal halide lamp is used as a light source, and exposure is performed so that the integrated light amount on the composition becomes 500 mJ / cm ² . Thereafter, development is carried out using a 1 wt% aqueous solution of Na ₂ CO _{3 at} a liquid temperature of 30 ° C., followed by washing with water. Lastly, after being left in air at 450 ° C. for 30 minutes, it is baked in air at 530 ° C. for 30 minutes.

Substrate preparation method 2: For the glass paste composition prepared in Example 5, an evaluation substrate was prepared under the following conditions. One hour after the preparation, the composition is applied to the entire surface of one side of the glass substrate using a 300 mesh polyester screen. Next, using a hot air circulation type drying furnace,
Dry at 80 ° C. for 10 minutes. Next, a line width of 50 μm
Using a negative film having a lattice pattern as follows, the light source was a metal halide lamp, and the integrated light amount on the composition was 500 m.
Exposure is performed so as to be J / cm ² . Next, it heats at 120 degreeC for 10 minutes using a hot air circulation type drying furnace. afterwards,
Development is carried out using a 1 wt% Na ₂ CO ₃ aqueous solution at a liquid temperature of 30 ° C., followed by washing with water. Finally, 30 minutes at 450 ° C in air.
After standing for a minute, baking is performed at 530 ° C. for 30 minutes in the air.

Performance Evaluation: (1) Storage Stability For each of the compositions prepared in Examples 1 to 4, the viscosity stability after 1 hour and 24 hours after the preparation was evaluated. (Example 5 is excluded because it has the same composition as Example 3 (only the substrate manufacturing method is different).) ：: stable Δ: tends to thicken

(2) Line Persistence The line persistence after development was evaluated for the evaluation substrates prepared using the compositions of Examples 1 to 5. ：: good △: partially dissolved

(3) Space Developability With respect to the evaluation substrates prepared using the compositions of Examples 1 to 5, the space developability between lines after development was evaluated. ：: good △: slight development residue ×: development not possible

(4) Line shape after firing The evaluation substrates prepared using the compositions of Examples 1 to 5 were evaluated for cracks in the fired pattern. ：: No crack △: Crack occurred

The evaluation results are shown in Table 1.

[Table 1]

[0052]

As described above, since the negative photosensitive glass paste composition of the present invention uses a resin in which a carboxyl group is blocked, it does not react with a glass frit to increase the viscosity and has excellent stability. In addition, a carboxylic acid is rapidly expressed by the catalytic action of an acid generated by thermal decomposition of the thermal acid generator during the heating step, and high resolution is exhibited. Further, since this polymer does not contain a double bond, curing shrinkage during firing is reduced. Therefore, in producing a plasma display panel, a high-definition partition wall pattern, a conductive circuit pattern,
A fired product pattern such as a black matrix pattern can be formed with high yield and high productivity.

[Brief description of the drawings]

FIG. 1 is a partially exploded perspective view of a surface discharge type AC PDP.

[Explanation of symbols]

 Reference Signs List 1 front glass substrate 2a, 2b display electrode 3a, 3b transparent electrode 4a, 4b bus electrode 5 dielectric layer 6 protective layer 11 rear glass substrate 12 rib 13 address electrode 14a, 14b, 14c phosphor film

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01J 9/20 H01J 9/20 A 11/02 11/02 B // C09D 4/00 C09D 4/00

Claims (9)

[Claims] (A) a weight average molecular weight of 1,000 to 5 having two or more groups represented by the following general formula (1) in a side chain:
000 polymer, (B) a compound that generates radicals by irradiation with active energy rays, (C) a compound that generates an acid by heating, (D) a photopolymerizable monomer, (E) a diluting solvent, and (F) 2.) An alkali-developable photosensitive glass paste composition comprising a glass frit. Embedded image (A) a weight average molecular weight of 1,000 to 5 having two or more groups represented by the following general formula (1) in a side chain:
000 polymer, (B) a compound that generates a radical by irradiation with active energy rays, (C) a compound that generates an acid by heating, (D) a photopolymerizable monomer, (E) a diluting solvent, (F) An alkali-developable photosensitive glass paste composition comprising: a glass frit; and (G) an inorganic powder other than the glass frit. Embedded image 3. The composition according to claim 2, wherein the inorganic powder (G) contains at least one of a ceramic powder, a black pigment, and a conductive metal powder. 4. The polymer (A) has a solid content acid value of 60.
The resin according to any one of claims 1 to 3, wherein a carboxyl group of the polycarboxylic acid resin of ~ 300 mgKOH / g is blocked with a group represented by the general formula (1). Composition. 5. The composition according to claim 4, wherein the polycarboxylic acid resin is a copolymer resin of acrylic acid or methacrylic acid at 8 to 40% by weight and another monomer. 6. The reaction compound for blocking a carboxyl group of the polycarboxylic acid resin has a boiling point of 30 to
The composition according to claim 4, wherein the composition is a monovinyl ether compound at 200 ° C. 7. 7. The glass frit (F) is a glass frit having a glass transition point of 300 to 550 ° C., and the black pigment contains at least two oxides of Cu, Fe, Cr, Mn, and Co as main components. The composition according to any one of claims 3 to 6, wherein the composition is a metal oxide pigment, and contains 3 to 50 parts by weight of the metal oxide pigment per 100 parts by weight of the glass frit (F). . 8. A step of applying the photosensitive glass paste composition according to any one of claims 1 to 7 to a substrate, wherein the applied layer is heated and dried to form a tack-free coating film and at the same time an acid is applied. Generating a carboxylic acid by deblocking the side chain of the polymer (A); selectively irradiating the coating film with an active energy ray; And baking the pattern after development. 9. A step of applying the photosensitive glass paste composition according to any one of claims 1 to 7 to a substrate, a step of heating and drying the applied layer to form a tack-free coating film, Selectively irradiating the coating film with an active energy ray, heating the coating film after the irradiation, deblocking a side chain of the polymer (A) to express a carboxylic acid,
A method for forming a fired product pattern, comprising a step of developing and removing a coating film of the non-irradiated portion with an aqueous alkali solution and a step of firing the developed pattern.