JP2000305265A - Photosensitive paste composition and panel having pattern calcined by using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive paste composition superior in photocurability and resolution and capable of fabricating a pattern high in aspect ratio and precision and to provide a plasma display panel(PDP) having the desired calcined pattern formed by using this paste composition. SOLUTION: This photosensitive paste composition comprises (A) fine inorganic particles, (B) an organic component containing a photopolymerizable compound, (C) a cationic dye represented by formula I: D+.A- (D+ is a cation having absorption in an optional wavelength region from the visible light to the near infrared region and A- is one of various kinds of anions, and (D) an organic boron compound represented by the formula in which each of R1-R4 is respectively alkyl, aryl, aralkyl, alkenyl, silyl, or heterocyclic or aliphatic group or a halogen atom; and Z+ is a cation. The desired calcined pattern, such as a partition wall pattern and a dielectric pattern and an electrode pattern of PDP can be produced in good productivity by the liftoff method or the photolithographic method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive pattern useful for forming a partition (barrier rib) pattern of a plasma display panel (hereinafter abbreviated as PDP), a dielectric pattern, an electrode (conductor circuit) pattern, and a black matrix. The present invention relates to a paste composition and a panel on which a fired product pattern is formed using the paste composition.

[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 grid-like 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 a structural example of a surface discharge type PDP having a three-electrode structure for full color display. On a 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 reducing 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 the display electrode, maintaining a discharge state, and the like.

On the other hand, on the back glass substrate 7, stripe-shaped ribs (partitions) 8 for dividing discharge spaces and address electrodes (data electrodes) 9 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 (10a), green (10b), and blue (10c) are regularly arranged. In the full-color display, one pixel is constituted by the phosphor films of the three primary colors of red, green and blue 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 10a, 10b, and 10c of the rear substrate 7, and the generated visible light is viewed through the transparent electrodes 3a and 3b of the front substrate 1 (reflection). Type).

In recent years, there has been an increasing demand for higher density and higher definition in pattern processing of circuit boards and displays, and accordingly, high reliability and high definition pattern formation is also required for materials and pattern processing techniques. ing. In particular, in forming a partition wall of a plasma display panel, it is desired to pattern a composition such as glass having a high inorganic component ratio with a high definition and a high aspect ratio.

[0006] As a conventional pattern forming method of the PDP partition wall, various methods such as a screen printing method, a sand blast method, a lift-off method (also referred to as a dry film embedding method) are known. However, screen printing is
There are problems such as skill, bleeding and blurring during printing, and alignment accuracy due to the expansion and contraction of the screen, and the yield is low. In addition, since there is a limit to the film thickness that can be obtained by one printing, there is a problem that a large number of superposition printings are required to form a partition having a high aspect ratio, resulting in poor workability.

Accordingly, a photolithography method has been proposed as a method of forming a partition wall which can be substituted for the screen printing method (see Japanese Patent Application Laid-Open No. 2-165538). However, since the sensitivity and resolution of the photosensitive paste are low, a plurality of processing steps (printing, exposure, and development) are required to obtain a high-aspect-ratio thick pattern as in the case of the screen printing method. Had the problem of becoming longer. That is, the photosensitive composition has no problem when a relatively thin film is formed, but when the film thickness is large, depending on the exposure conditions, the resolution after development is insufficient due to insufficient photocuring depth at the time of exposure. In some cases, problems such as poor properties may occur, and problems such as pattern distortion, line width shrinkage, and warpage may occur during firing. In particular, the photosensitive paste composition used for forming a fired product pattern such as a partition pattern, a conductor pattern, and a dielectric pattern contains an extremely large amount of inorganic powder such as glass fine particles or metal fine particles having an extremely small particle size. Therefore, the light transmittance during exposure is poor, so that the photocuring becomes insufficient, and the photocuring unevenness is also apt to occur, and such a phenomenon is caused as the film thickness increases and the film becomes deeper. It is easy to appear. Therefore, in order to form a thick pattern, it is necessary to repeat the above steps, and there is a problem in workability, accuracy, and the like.

On the other hand, in the sand blast method, a glass paste is applied to the entire surface of a substrate to a predetermined thickness, a photosensitive dry film having blast resistance is overlaid thereon, and then the photosensitive film is patterned into a partition shape. Thereafter, a method of spraying abrasive powder to scrape off the glass paste portion not covered with the film is used. With this method, it is possible to form a high-definition partition wall, but there is a problem that a large amount of grinding powder is generated, which deteriorates the working environment and reduces the yield. In addition, when the screen is scaled up to a large screen, it becomes difficult to uniformly form partitions having the same dimensions over the entire surface.

In the lift-off method, even if the photosensitive dry film used has a film thickness of about 200 μm, it is easy to pattern it with a large screen of a diagonal size of 40 inches and uniform dimensions, and this feature can be used for panel production. it can. In the partition formation by the lift-off method, first, after laminating a photosensitive dry film of a predetermined thickness on a transparent glass substrate on which a lower member such as an electrode is formed, a photomask having a predetermined partition shape pattern is overlapped. Thereafter, exposure and development are performed, and a portion of the photosensitive film that has not been exposed through a photomask is removed to form a groove. Next, the above-mentioned exposure, the grooves of the photosensitive film formed by the development, the glass paste is applied so as to be embedded, dried and heated and cured, then the removal of the photosensitive film and firing of the glass paste, It forms a partition. Since the partition walls formed by this method are superior in dimensional stability as compared with the above-described screen printing method and sand blast method, they are attracting attention as a method capable of producing high-definition partition walls for PDP with a high yield.

However, in the lift-off method, glass paste is generally buried in grooves of the photosensitive film, defoaming under reduced pressure, and drying are performed prior to heat curing. Since the glass paste sinks due to the volatilization of the solvent component in the above, it is necessary to repeat the embedding-defoaming-drying cycle several times, which leads to a complicated process and one of the factors that lowers the productivity.
Thereafter, a heat treatment for curing is further performed, and after the photosensitive film is peeled off with a release agent, high-temperature heating for firing is performed. Since a large number of heating steps are required as described above, the production steps are complicated and energy consumption is increased, which is a factor for increasing the production cost.

[0011]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and in particular, a photosensitive paste capable of processing a pattern with a high aspect ratio and high precision. It is intended to provide a composition. Another object of the present invention is to provide a photosensitive paste composition exhibiting an excellent photocuring depth in addition to the above characteristics. Still another object of the present invention is to provide a panel in which a desired baked product pattern of a PDP is formed using the photosensitive paste composition, and a method for manufacturing the same.

[0012]

According to the present invention, there is provided, according to the present invention, (A) an inorganic fine particle, (B) an organic component containing a photopolymerizable compound, (C) the following general formula (1): And (D) an organic boron compound represented by the following general formula (2). Formula ^{(1): D + · A} - ( wherein, D ⁺ is a cation having an absorption in the desired wavelength region of from visible light to near infrared light, A ^- represents various anions.) General formula (2):

Embedded image (Wherein, R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group, a silyl group, a heterocyclic group, an alicyclic group or a halogen atom;
⁺ Indicates a cation. )

Further, according to the present invention, a plasma display panel (PDP) in which a desired baked product pattern such as a partition pattern, a derivative pattern, an electrode pattern, a black matrix pattern or the like is formed using the photosensitive paste composition as described above. Is provided. The method is characterized in that it includes a step of forming a pattern by a lift-off method or a photolithography method using the photosensitive paste composition, followed by baking.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive paste composition according to the present invention mainly comprises a large amount of inorganic fine particle components and an organic component containing a photopolymerizable compound, and forms a pattern by photo-curing of the photosensitive organic component. After that, firing is performed to form an inorganic fired product pattern. We have:
The problems of photocurability, productivity and the like as described above are caused by the fact that in a photosensitive paste composition containing a large amount of inorganic fine particle components, (C) a cationic dye represented by the general formula (1) (D) The present invention has been found to be greatly improved by adding the organic boron compound represented by the general formula (2), and has completed the present invention. The organic boron compound is decomposed by light to form a radical as shown by the following formula.

Embedded image Further, when a cationic dye coexists, electron transfer occurs between the dye molecule and the dye molecule excited by light absorption of the cationic dye,
Radical generation efficiency increases. Therefore, by selecting a cationic dye and an organoboron compound, it is sensitive in the visible to near-infrared light region and becomes a highly sensitive radical generating source. That is, the photosensitive paste composition of the present invention,
(C) Since it contains a combination of the cationic dye represented by the general formula (1) and the organic boron compound represented by (D) the organic boron compound represented by the general formula (2), it has a longer wavelength region than the conventional UV initiator. (Visible light region of 400 nm or more). Therefore, the photocurability of the photosensitive paste composition is greatly improved, and even when the film is thick, photocuring can sufficiently proceed to the deep portion of the formed film, and warpage and line width shrinkage during firing can be reduced. It is hard to occur, and high-aspect-ratio and high-precision pattern processing becomes possible. Also,
In the case of the same film thickness, the exposure amount can be made smaller than before, and energy saving can be realized.

As described above, the photosensitive paste composition according to the present invention comprises (A) inorganic fine particles, (B) an organic component containing a photopolymerizable compound, and (C) a positive electrode represented by the general formula (1). It contains an ionic dye and (D) an organic boron compound represented by the general formula (2) as essential components.
The contents of the components (A) and (B) differ depending on the desired fired product pattern, and also differ depending on the pattern forming method. First, as the inorganic fine particles of the component (A), glass fine particles are used in the case of forming a partition pattern and a dielectric pattern, and glass fine particles and a black pigment are used in the case of a black matrix pattern. On the other hand, in the case of forming an electrode pattern, a conductive powder (conductive metal powder and / or metal oxide) is used, but an appropriate amount of glass fine particles may be used in combination to improve sinterability as described later. Preferably, when a black electrode pattern is formed, a black pigment is further used. Others
Aggregates (inorganic fillers) can be added to the photosensitive paste composition as desired.

Next, the "organic component containing a photopolymerizable compound" of the component (B) means that a photopolymerizable component is contained as an essential component. Examples of the photopolymerizable component include (B-1) a photosensitive monomer, oligomer, and / or polymer, and (B-3) a carboxyl group-containing photosensitive resin (oligomer or polymer), and a photosensitive binder (photosensitive Prepolymer). Optional organic components include solvents and dispersants useful for pasting compositions. When a dispersant is used, it can be easily formed into a paste without using an organic solvent, so that there is an advantage that the composition can be formed into a solventless paste. Other optional organic components include a binder, the component (C) and the component (D).
Other than the components, a photopolymerization initiator, a photosensitizer, a stabilizer, a defoaming / leveling agent, a silane coupling agent, an antioxidant and the like can be mentioned.

When a lift-off method is used as a pattern forming method, a developing step is not required, and it is not necessary to use a photopolymerizable component or an organic binder having a carboxyl group as described later. However,
Use of a photopolymerizable component having a carboxyl group or an organic binder does not matter at all. However, when photolithography is used for pattern formation and development is performed using an aqueous alkali solution, a photosensitive resin (oligomer or polymer) used as a photopolymerizable component may be a resin having a carboxyl group or may be an organic resin. Either an alkali-soluble binder is used as the binder, or any countermeasure is required.

Hereinafter, each component of the photosensitive paste composition of the present invention will be described. The glass fine particles in the inorganic fine particles (A) may have a glass transition point (Tg) of 300 to
Those having a temperature of 500 ° C. and a glass softening point (Ts) of 400 to 600 ° C., for example, those mainly containing lead oxide, bismuth oxide or zinc oxide can be suitably used. From the viewpoint of resolution, glass fine particles having an average particle size of 10 μm or less are preferable. An appropriate amount of the glass fine particles is such that the total amount of the components in the paste other than the glass fine particles is 50 to 2,000 parts by weight based on 100 parts by weight.

As a preferred example of the glass fine particles containing lead oxide as a main component, PbO is 48% by weight on an oxide basis.
~82%, B ₂ O ₃ is 0.5 to 22%, SiO ₂ is 3-3
_2%, Al 2 O ₃ is 0 to 12%, BaO is 0%, Z
nO is 0 to 15%, TiO ₂ is 0~2.5%, Bi ₂ O ₃
Has a composition of 0 to 25% and a softening point of 420 to 590 ° C.
And a non-crystalline frit.

[0020] Preferred examples of the glass fine particle mainly comprising bismuth oxide, in weight percent on the oxide basis, Bi ₂
O ₃ is 35 to 88%, B ₂ O ₃ is 5 to 30%, SiO ₂ 0
To 20% Al ₂ O ₃ is 0 to 5% BaO 1 to 25%
ZnO has a composition of 1 to 20% and a softening point of 420 to 5
A noncrystalline frit that is 90 ° C.

As a preferred example of the glass fine particles containing zinc oxide as a main component, ZnO is 2% by weight based on the oxide.
5~60%, K ₂ O is 2~15%, B ₂ O ₃ is 25 to 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.

As the inorganic filler in the inorganic fine particles (A), any of inorganic fillers such as alumina, silica, zircon, titanium oxide and the like which can contribute to the improvement of the density inside the fired product pattern such as partition walls can be used. That is, although the glass component shrinks during firing, the shrinkage and the internal density can be adjusted by the amount of the inorganic filler. That is, by blending the inorganic filler in an amount of 0.1 to 50 parts by weight per 100 parts by weight of the glass fine particles, it is possible to obtain a fired product pattern such as a partition wall which is dense and has a small shrinkage ratio. In this case, if the amount of the inorganic filler is more than the above range, the adhesiveness to the substrate is deteriorated, which is not preferable.

The black pigment in the inorganic fine particles (A) is used when a fired product pattern is required to be black, and may be one or more metal oxides such as Fe, Co, Ni, Cu, Mn, and Al. Black pigments can be added. An appropriate amount of the black pigment is 10 to 100 parts by weight per 100 parts by weight of the glass fine particles.

The conductive metal powder or metal oxide in the inorganic fine particles (A) has a specific resistance of 1 × 10 ³ Ω ·
cm or less can be used as long as the conductive powder is silver (Ag), gold (Au), nickel (Ni), copper (Cu), aluminum (Al), tin (Sn), and lead (P).
b), zinc (Zn), iron (Fe), platinum (Pt), iridium (Ir), osmium (Os), palladium (P
d), rhodium (Rh), ruthenium (Ru), tungsten (W), molybdenum (Mo) and the like and their alloys, as well as tin oxide (SnO ₂ ) and indium oxide (In ₂ O)
₃ ), ITO (Indium Tin Oxide), ruthenium oxide (RuO ₂ ) and the like can be used. These can be used alone or as a mixed powder of two or more.

As the shape of the conductive metal powder or metal oxide, various shapes such as a sphere, a flake, and a dendrite can be used. . The average particle diameter is preferably 20 μm or less, more preferably 5 μm or less, from the viewpoint of resolution. Further, in order to prevent oxidation of the conductive metal powder, improve dispersibility in the composition, and stabilize developability, it is particularly preferable to treat Ag, Ni, and Al with a fatty acid. As fatty acids,
Oleic acid, linoleic acid, linolenic acid, stearic acid and the like can be mentioned.

The amount of the conductive metal powder to be mixed is 100% of the total amount of the components in the paste other than the conductive metal powder or the metal oxide.
A suitable ratio is 50 to 2,000 parts by weight in terms of parts by weight. When the compounding amount of the conductive metal powder or the metal oxide is less than 50 parts by weight, the line width of the conductor circuit is likely to shrink or break, whereas when the compounding amount is more than 2,000 parts by weight, light transmission is caused. And it becomes difficult to obtain sufficient photocurability of the composition. Further, in order to improve the strength of the film after firing and the adhesion to the substrate, the above glass fine particles can be added at a ratio of 1 to 30 parts by weight per 100 parts by weight of the metal powder.

As the organic component (B) containing a photopolymerizable compound, (B-1) at least one (meth)
(B-2) a carboxyl group-containing weight-average molecular weight of 1,000 to 100,000 and an acid value of 2
Oligomer or polymer of 0 to 150 mgKOH / g, (B-3) weight average molecular weight having a carboxyl group and an ethylenically unsaturated group of 1,000 to 100,000, acid value of 20 to 150 mgKOH / g, and double bond equivalent thereof , A binder, a photopolymerization initiator, a photosensitizer, an organic solvent, a stabilizer, a silicone-based and acrylic-based defoaming / leveling agent, and a silane cup. Contains organic components in the paste, such as ring agents, antioxidants, which are
It can be arbitrarily selected according to the necessity of the intended photocurable pattern forming method.

As a typical example of the photosensitive monomer, oligomer and / or polymer having at least one (meth) acryloyl group in one molecule of (B-1), 2
Hydroxyalkyl (meth) acrylates such as -hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; mono- or di (meth) acrylates of glycol such as ethylene glycol, methoxytetraethylene glycol and polyethylene glycol; N (Meth) acrylamides such as N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; aminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate;
Polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and trishydroxyethyl isocyanurate, and polyhydric (meth) acrylates of ethylene oxide adduct or propylene oxide adduct thereof; phenoxy Ethylene oxide adducts of phenols such as ethyl (meth) acrylate and polyethoxydi (meth) acrylate of bisphenol A or (meth) acrylates of propylene oxide adducts; glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanate (Meth) acrylates of glycidyl ether such as nurate; and melamine (meth) acrylate, urethane (meth ) Such as acrylates, and the like. In this specification, the term “(meth) acrylate” is a general term for acrylate, methacrylate and mixtures thereof, and the same applies to other similar expressions.

The oligomers or polymers (B-2) and (B-3) include a carboxyl group-containing resin having no ethylenically unsaturated double bond and a resin having an ethylenically unsaturated double bond itself. It is a carboxyl group-containing photosensitive resin. Preferred examples of the resin (which may be any of an oligomer and a polymer) include the following. (1) reacting a copolymer of (a) an unsaturated carboxylic acid and (b) a compound having an unsaturated double bond with an ethylenically unsaturated compound having a functional group that reacts with a carboxyl group;
Carboxyl group-containing photosensitive resin having an ethylenically unsaturated group as a pendant (2) (c) a copolymer of a compound having a glycidyl group and an unsaturated double bond and (b) a copolymer of a compound having an unsaturated double bond, (A) a carboxyl group-containing photosensitive resin obtained by reacting an unsaturated carboxylic acid with (d) a polybasic anhydride to react with a secondary hydroxyl group generated (3) (e) forming an unsaturated double bond Acid anhydride having (b)
(F) a carboxyl group-containing photosensitive resin obtained by reacting a copolymer of a compound having an unsaturated double bond with (f) a compound having a hydroxyl group and an unsaturated double bond; A) a carboxyl group-containing photosensitive resin obtained by reacting (d) a polybasic acid anhydride with a secondary hydroxyl group produced by reacting an unsaturated monocarboxylic acid; (5) (b) having an unsaturated double bond In the glycidyl group of the copolymer of the compound and glycidyl (meth) acrylate,
(I) An organic acid having one carboxyl group in one molecule and having no ethylenically unsaturated bond is reacted, and the resulting secondary hydroxyl group is reacted with (d) a polybasic acid anhydride. Carboxyl group-containing resin (6) Carboxyl group-containing resin obtained by reacting (j) hydroxyl group-containing polymer with (d) polybasic acid anhydride (7) (j) Hydroxy group-containing polymer with (d) polybasic acid anhydride To the carboxyl group-containing resin obtained by reacting
(C) Carboxyl group-containing photosensitive resin obtained by further reacting a compound having an unsaturated double bond with a glycidyl group

As an example of the carboxyl group-containing photosensitive resin (1), a part of the carboxyl group of the copolymer of the unsaturated carboxylic acid (a) and the compound (b) having an unsaturated double bond may be For example, there is a resin in which glycidyl (meth) acrylate is reacted at a rate that improves photocurability to such an extent that a sufficient photocuring depth is obtained, and an unsaturated double bond of the glycidyl (meth) acrylate is introduced into a side chain. . Since a part of the carboxyl group of the unsaturated carboxylic acid (a), which is one monomer component of the copolymer, remains unreacted, the resulting carboxyl group-containing photosensitive resin is soluble in an aqueous alkali solution. It is. for that reason,
A film formed from the photosensitive paste composition containing such a resin can be stably developed with an aqueous alkali solution after selective exposure.

Specific examples of the unsaturated carboxylic acid (a) include acrylic acid, methacrylic acid, itaconic acid,
Crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, or an acid anhydride thereof; further, an acid anhydride such as maleic anhydride, itaconic anhydride, or pyromellitic anhydride, and 2-hydroxyethyl (meth) acrylate; Reaction products with an unsaturated compound having a hydroxyl group such as hydroxyalkyl (meth) acrylates such as -hydroxypropyl (meth) acrylate; and these can be used alone or in combination of two or more. Among these, acrylic acid and / or methacrylic acid are preferred.

Compound (b) having an unsaturated double bond
Specific examples of styrene, chlorostyrene and α-methylstyrene; methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and ter as substituents
t-butyl, amyl, 2-ethylhexyl, octyl,
(Meth) acrylate having capryl, nonyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isobornyl, methoxyethyl, butoxyethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-chloro-2-hydroxypropyl and the like; polyethylene glycol mono Mono (meth) acrylate of (meth) acrylate or polypropylene glycol; vinyl acetate, vinyl butyrate, vinyl benzoate; acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-
Hydroxymethyl methacrylamide, N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide, N-butoxymethyl acrylamide, acrylonitrile, vinyl ethers, isobutylene and the like, and these may be used alone or in combination of two or more. it can. Among these compounds, styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene are preferably used, and methyl methacrylate is particularly preferable from the viewpoint of thermal decomposability of the resin.

Examples of the pendant having an ethylenically unsaturated group include a vinyl group, an allyl group, an acryloyl group and a methacryloyl group. The method of giving such a pendant to the copolymer is generally a method of adding an ethylenically unsaturated compound having a glycidyl group or (meth) acrylic acid chloride to a carboxyl group of the copolymer. Examples of the ethylenically unsaturated compound having a glycidyl group and (meth) acrylic acid chloride include glycidyl (meth) acrylate, allyl glycidyl ether, α-methyl glycidyl (meth) acrylate, α-ethyl glycidyl (meth) acrylate, Glycidyl crotonic acid ether, glycidyl ether isocrotonic acid, (meth) acrylic acid chloride, (meth)
Examples include allyl chloride and compounds represented by the following general formulas (3) to (6). Of these, glycidyl (meth) acrylate is preferred.

Embedded image

The carboxyl group-containing photosensitive resin (2) is a copolymer of (c) a compound having a glycidyl group and an unsaturated double bond in the molecule and (b) a compound having an unsaturated double bond. In order to improve the photocurability to the extent that a sufficient photocuring depth can be obtained, the carboxyl group of the (a) unsaturated carboxylic acid is reacted with the epoxy group of
The unsaturated double bond of the unsaturated carboxylic acid is introduced into the side chain, and (d) is added to the secondary hydroxyl group generated by the above addition reaction.
It is a resin in which a carboxyl group is introduced into a side chain by subjecting a polybasic acid anhydride to an esterification reaction.

Specific examples of the compound (c) containing a glycidyl group and an unsaturated double bond in the molecule include glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate, and compounds of the above formulas (3) to (3). The compounds represented by (6) and the like can be mentioned, and these can be used alone or in combination of two or more. On the other hand, specific examples of the polybasic anhydride (d) include succinic anhydride, maleic anhydride, adipic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Examples include itaconic acid, methylendomethylenetetrahydrophthalic anhydride, trimellitic anhydride, and pyromellitic anhydride, and these can be used alone or in combination of two or more.

The carboxyl group-containing photosensitive resin of (3) is an acid anhydride of a copolymer of (e) an acid anhydride having an unsaturated double bond and (b) a compound of a compound having an unsaturated double bond. In order to improve photocurability to such an extent that a sufficient photocuring depth can be obtained, part of the groups are reacted with a hydroxyl group of a compound having a hydroxyl group and an unsaturated double bond to form a half ester, It is a resin in which the unsaturated double bond of compound (f) is introduced into a side chain.

Specific examples of the acid anhydride (e) having an unsaturated double bond include maleic anhydride, itaconic anhydride, and pyromellitic anhydride and 2-hydroxyethyl (meth) acrylate, And partial reaction products with an unsaturated compound having a hydroxyl group such as hydroxyalkyl (meth) acrylates such as -hydroxypropyl (meth) acrylate. These can be used alone or in combination of two or more. . Among these, maleic anhydride which can stably synthesize a polymer is preferable.

Specific examples of the compound (f) having a hydroxyl group and an unsaturated double bond include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; A monomer obtained by reacting caprolactone with (meth) acrylic acid; a macromonomer obtained by reacting polycaprolactone oligomer with (meth) acrylic acid;
These can be used alone or in combination of two or more. The carboxyl group-containing photosensitive resins (1) to (3) as described above have excellent photocurability and baking properties, and contribute to the storage stability of the composition.

The carboxyl group-containing photosensitive resin (4) is used to improve the photocurability of the epoxy group of the epoxy compound (g) to such an extent that a sufficient photocuring depth can be obtained. The carboxyl group of the saturated monocarboxylic acid is reacted to produce, for example, an epoxy acrylate, and the secondary hydroxyl group formed by the above addition reaction is subjected to an esterification reaction with the polybasic acid anhydride (d). Is a resin into which is introduced. Such a carboxyl group-containing photosensitive resin has excellent photocurability,
The backbone polymer epoxy acrylate exhibits hydrophobicity. Therefore, when a photosensitive paste composition containing the resin is used, the hydrophobicity of the epoxy acrylate is advantageously used, and the development resistance of a deep portion of the pattern that is hard to be photocured is improved. As a result, the latitude in setting conditions in the development and exposure steps is increased, the yield during mass production can be improved, and the occurrence of curling of the pattern edge after firing can be significantly reduced, and a high aspect ratio, high definition pattern can be formed. . In addition, an acrylic copolymer resin that is easily depolymerized by heat during baking is mixed with the carboxyl group-containing photosensitive resin, thereby lowering the sintering temperature of the photosensitive paste composition, and in all the resins used, The double bond concentration can also be adjusted.

As the epoxy compound (g), all epoxy resins can be used. Typical examples thereof include bisphenol A type, hydrogenated bisphenol A type, bisphenol F type, bisphenol S type, and phenol novolak. And epoxy compounds such as cresol novolak type, novolak type of bisphenol A, biphenol type, bixylenol type, N-glycidyl type and the like.
PE-3150 and the like, and these can be used alone or in combination of two or more.

Specific examples of the unsaturated monocarboxylic acid (h) include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacryl Acid, β-furfurylacrylic acid and the like, and these can be used alone or in combination of two or more.

In the reaction of the epoxy compound (g) with the unsaturated monocarboxylic acid (h), the number of equivalents of epoxy group / the number of equivalents of carboxyl group is 0.8 to 1.2, preferably 0.9 to 1.2.
It is preferable to carry out at a ratio of up to 1.05. If the number of equivalents of the epoxy group / the number of equivalents of the carboxyl group is less than 0.8, there is a problem of odor because the unsaturated monocarboxylic acid remains. On the other hand, if the number of equivalents exceeds 1.2, the number of epoxy groups becomes large. Since it remains, it is not preferable because gelation easily occurs at the stage of reacting the polybasic acid anhydride. Also, the generated 2
The reaction ratio of the polybasic acid anhydride to the hydroxyl group of the grade, the acid value of the finally obtained resin is preferably 30 to 160 mg
Adjust so as to be within the range of KOH / g. Generally, the equivalent of the polybasic anhydride is 0.3 or more, preferably 0.5 or more, per 1 equivalent of the hydroxyl group generated by the reaction between the epoxy compound and the unsaturated monocarboxylic acid.

The carboxyl group-containing resin (5) is
(B) Glycidyl of a copolymer having an unsaturated double bond and having no hydroxyl group or acidic group, such as an alkyl (meth) acrylate, substituted or unsubstituted styrene, and glycidyl (meth) acrylate as a main chain. Based on (i)
An organic acid having one carboxyl group in one molecule and having no ethylenically unsaturated bond is reacted, and the resulting secondary OH group is subjected to the addition reaction of the above-mentioned polybasic acid anhydride (d). Resin. The introduction of a carboxyl group in this resin is carried out by reacting an organic acid with a glycidyl group of the pendant of the above copolymer, and adding a polybasic acid anhydride to a secondary hydroxyl group located near the main chain. The carboxyl group is bonded to the site near the main chain of the side chain, and the steric hindrance between the main chain and the side chain controls the contact between basic glass particles and conductive metal powder. Is done. As a result, a composition containing such an alkali-soluble carboxyl group-containing resin together with glass fine particles and conductive metal powder exhibits excellent storage stability, and almost no change in viscosity or gelation occurs during storage. Absent.

Organic acid (i) having one carboxyl group in one molecule and having no ethylenically unsaturated double bond
Acetic acid, propionic acid, n-butyric acid, iso-butyric acid, n-dimethylbutyric acid, ethylbutyric acid, hexanoic acid, 2-
Methylpentanoic acid, 2-ethylpentanoic acid, heptanoic acid, 2-methylheptanoic acid, lauric acid, stearic acid, n-heptadecanoic acid and the like, alkyl carboxylic acids having 2 to 17 carbon atoms, or substituted or unsubstituted benzoic acids,
(R), (S) -2-phenylpropionic acid, (R)-
Aromatic group-containing alkyl carboxylic acids such as phenylisopropionic acid, 2-phenylbutyric acid, and 4-phenylbutyric acid are listed, and these can be used alone or in combination of two or more.

The carboxyl group-containing resin (6) is
(J) A resin in which a carboxyl group is introduced by reacting the polybasic acid anhydride (d) having relatively weak acidity with a hydroxyl group-containing polymer. Since such a carboxyl group-containing resin contains a hydrophilic group (carboxyl group, hydroxyl group), it exhibits good wettability to a substrate, and is easily thermally decomposed at a high temperature, and contains a photosensitive paste composition containing the same. Shows stable adhesion to the substrate and good storage stability in each of the steps of drying, exposure, development and baking, and also has excellent baking properties.

On the other hand, the carboxyl group-containing photosensitive resin of (7) is added to the carboxyl group of the carboxyl group-containing resin (6) in such a ratio that the photocurability is improved to such an extent that a sufficient photocurable depth is obtained. And (c) a resin obtained by reacting the glycidyl group with an epoxy group of a compound having an unsaturated double bond to introduce the unsaturated double bond of the compound (c) into a side chain. Such a carboxyl group-containing photosensitive resin is excellent in photocurability, and shows a sufficient photocuring depth even when it is mixed with a large amount of inorganic fine particles to form a paste composition. In addition, the composition has excellent baking properties and contributes to improving the storage stability of the composition.

As the hydroxyl group-containing polymer (j),
Olefinic hydroxyl group-containing polymer, acrylic polyol, rubber polyol, polyvinyl acetal resin,
A styrene allyl alcohol-based resin, a cellulose-based resin, or the like can be used. As the olefinic hydroxyl group-containing polymer, polyethylene, polypropylene, polybutadiene or the like as a main chain, a resin having a hydroxyl group in the main chain or a side chain can be used, or a copolymer of allyl alcohol and ethylene or butadiene is used. be able to.

Specific examples of the acrylic polyol include:
LR2507, LR2516, manufactured by Mitsubishi Rayon Co., Ltd.
LR257, LR989, LR2536, LR532,
LR598, LR566, LR286, LR511, L
R2528 and the like. Specific examples of the rubber polyol include Unistor P901, manufactured by Mitsui Petrochemical Co., Ltd.
Kuraray Co., Ltd. Kuraprene LIR-506, TL-2
0, TH-1 TH-21, TH-31, Clapol P-
510, Kurapol P-15610, Kurapol P-5
010 and the like. Specific examples of the styrene allyl alcohol resin include RJ10 manufactured by Monsanto Co., Ltd.
0, RJ101, SAA10 manufactured by ARCO Chemical Co., Ltd.
0, SAA101 and the like.

As the polyvinyl acetal resin, polyvinyl butyral, polyvinyl acetal, polyvinyl formal, and the like can be used.
H and the like.

Examples of the cellulosic resin include cellulose esters of acids such as acetylcellulose and nitrocellulose obtained by esterifying a part of the hydroxyl groups of cellulose, and propionic acid, butyric acid, phosphoric acid, sulfuric acid and phthalic acid. Further, a mixed ester obtained by mixing an acid can be used. Further, examples of the cellulose ether include methyl cellulose, ethyl cellulose, benzyl cellulose, carboxymethyl cellulose and the like in which a part of the hydroxyl groups of cellulose is etherified.

As the hydroxyl group-containing polymer (j) to be used, any polymer other than the above can be used.
Those having a hydroxyl value of 50 to 250 mgKOH / g are preferred. Note that hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose acetate succinate, cellulose acetate hexahydrophthalate, hydroxypropylmethylcellulose acetate phthalate, hydroxypropylmethylcellulose hexahydrophthalate, etc., manufactured by Shin-Etsu Chemical Co., Ltd. ) Can be used.

The carboxyl group-containing photosensitive resin and carboxyl group-containing resin each have a weight average molecular weight of 1,000 to 100,000, preferably 5,
000-50,000, and acid value 20-150 mg KO
H / g, preferably 40 to 100 mg KOH / g, and in the case of a carboxyl group-containing photosensitive resin, its double bond equivalent is 350 to 2,000, preferably 400
~ 1,500 can be suitably used. If the molecular weight of the resin is lower than 1,000, the adhesion of the coating at the time of development is adversely affected. On the other hand, if the molecular weight is higher than 100,000, poor development tends to occur, which is not preferable. When the acid value is lower than 20 mgKOH / g, the solubility in an aqueous alkali solution is insufficient, and poor development is likely to occur. ) Is not preferred because dissolution occurs. Further, when the double bond equivalent of the photosensitive resin is smaller than 350, residues are apt to remain at the time of baking, while when it is larger than 2,000, the working margin at the time of development is narrow, and high exposure at the time of photocuring. It is not preferable because it requires an amount.

(B-1) Photosensitive monomers, oligomers and / or polymers having a (meth) acryloyl group as described above, (B-2) a carboxyl group-containing resin and (B-3) a carboxyl group-containing photosensitive resin May be used alone or as a mixture, but in any case, it is preferable to mix them in a proportion of 0 to 50% by weight of the total amount of the composition. In particular, the components (B-1) and (B-
3) It is preferable that the components are added in a total amount of 5% by weight or more of the total amount of the composition. If the amount of these photosensitive components is too small, the photocurability and the depth of photocuring are difficult to obtain, and patterning by selective exposure and development becomes difficult. On the other hand, if the amount is more than the above range, the pattern is likely to be distorted and the line width shrinks during firing, which is not preferable.

The binder in the organic component (B) containing the photopolymerizable compound is intended to improve the stability of the paste and the workability of the coating, and may be any of those having or not having photosensitivity itself. Good. However, the photosensitive monomer, oligomer and / or polymer having (B-1) (meth) acryloyl group and (B-1)
-3) When none of the carboxyl group-containing photosensitive resins is used, it is preferable to use a photosensitive binder. As the photosensitive binder, various conventionally known photosensitive resins (photosensitive prepolymers) having a photosensitive group such as an ethylenically unsaturated bond such as a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group or a propargyl group are used. be able to. On the other hand, as the binder having no photosensitivity, the above-mentioned hydroxyl group-containing polymer (j), a lactone-modified polymer in which lactone is added to these hydroxyl groups or amino groups, and both a hydroxyl group or an amino group and an unsaturated group are contained in one molecule. Examples include a homopolymer of a lactone-modified monomer obtained by adding a lactone to a hydroxyl group or an amino group of a monomer, and a copolymer of the lactone-modified monomer with another monomer having an unsaturated group.

The photopolymerization initiator used in combination with the cationic dye (C) and the organic boron compound (D), if necessary, includes a photopolymerizable compound which is sensitive to light in the ultraviolet to visible region. Any compound can be used as long as it initiates the reaction, and one or a combination of two or more conventionally known photopolymerization initiators or a combination with a photosensitizer can be used. Specific examples of typical photopolymerization initiators include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, Acetophenones such as 2,2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one;
Aminoacetophenones such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone and 1-chloroanthraquinone Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; Or xanthones, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-
Trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4
4-trimethylpentylphosphine oxide, 2,
Phosphine oxides such as 4,6-trimethylbenzoylphenyl phosphinate or bisacylphosphine oxides, various peroxides, dimethyl titanocene, diphenyl titanocene, bis (pentafluorophenyl) titanocene, bis (η5-cyclopentadiene) Enyl) -bis (2,6-difluoro-3- (1
H-pyr-1-yl) phenyl) titanium and other various titanocene-based photopolymerization initiators, ferrocenium salt-based initiators, aluminate complex-based initiators, halogen-based initiators, bisimidazole-based initiators, Examples include peroxide ester initiators, ketocoumarin initiators, and acridine initiators. Representative examples of photosensitizers include leuco dyes, N, N-dimethylaminobenzoic acid ethyl ester,
N, N-dimethylaminobenzoic acid isoamyl ester,
Tertiary amines such as pentyl-4-dimethylaminobenzoate, triethylamine and triethanolamine are exemplified. The amount of these photopolymerization initiators (the total amount in the case of a combination with a photosensitizer) is suitably from 0 to 20 parts by weight per 100 parts by weight of the photosensitive component in the paste.

The photosensitive paste composition of the present invention is formed into a paste by diluting the composition, enabling an easy coating process, and then drying to form a film. An amount of an organic solvent can be incorporated. 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 Propylene glycol monomethyl ether,
Glycol ethers such as dipropylene glycol monoethyl ether and triethylene glycol monoethyl ether; acetates such as ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate and propylene glycol monomethyl ether acetate Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha, alone or Two or more can be used in combination.

Further, the photosensitive paste composition of the present invention comprises:
In order to improve the storage stability of the composition, it is possible to add a metal which is a component of glass fine particles or conductive metal powder, or a compound having an effect of complexing with an oxide powder or forming a salt. Specific examples include acids such as inorganic acids, organic acids, and phosphoric acid compounds (inorganic phosphoric acid, organic phosphoric acid). Such a stabilizer is preferably added at a ratio of 0 to 5 parts by weight per 100 parts by weight of the inorganic fine particles (A).
Examples of the inorganic acid include nitric acid, sulfuric acid, hydrochloric acid, boric acid and the like. Further, as the organic acid, formic acid, acetic acid, acetoacetic acid, citric acid, isocitric acid, anisic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, azelaic acid, caproic acid, isocaproic acid, enanthic acid, Caprylic acid, pelargonic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, arachinic acid, behenic acid (behenic acid), oxalic acid,
Malonic acid, ethyl malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, pyruvic acid, piperonyl acid, pyromellitic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid,
Terephthalic acid, tartaric acid, levulinic acid, lactic acid, benzoic acid,
Isopropyl benzoic acid, salicylic acid, isocaproic acid,
Crotonic acid, isocrotonic acid, acrylic acid, methacrylic acid, tiglic acid, ethylacrylic acid, ethylidenepropionic acid, dimethylacrylic acid, citronellic acid, undecenoic acid, undecanoic acid, oleic acid, elaidic acid, erucic acid, brassic acid, phenyl Acetic acid, cinnamic acid, methylcinnamic acid, naphthoic acid, abietic acid, acetylenedicarboxylic acid, atrolactic acid, itaconic acid, crotonic acid, sorbic acid, vanillic acid, palmitic acid, hydroxycinnamic acid, hydroxynaphthoic acid, hydroxybutyric acid ,
Biphenyldicarboxylic acid, phenylcinnamic acid, phenylacetic acid, phenylpropiolic acid, phenoxyacetic acid, propiolic acid, hexanoic acid, heptanoic acid, veratric acid, benzylic acid, oxalosuccinic acid, oxaloacetic acid, octanoic acid, gallic acid, mandelic acid, Mesaconic acid, methylmalonic acid, melitic acid, lauric acid, ricinoleic acid, linoleic acid, malic acid and the like.

As the inorganic phosphoric acid, phosphoric acid, phosphorous acid,
Hypophosphorous acid, orthophosphoric acid, diphosphoric acid, tripolyphosphoric acid, phosphonic acid and the like can be mentioned. Further, as the organic phosphoric acid, methyl phosphate, ethyl phosphate, propyl phosphate,
Butyl phosphate, phenyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dipropyl phosphate, diphenyl phosphate, isopropyl phosphate, diisopropyl phosphate, nbutyl phosphate, methyl phosphite, ethyl phosphite , Propyl phosphite, butyl phosphite, phenyl phosphite, dimethyl phosphite, diethyl phosphite, dibutyl phosphite, dipropyl phosphite, diphenyl phosphite,
Isopropyl phosphite, diisopropyl phosphite, nbutyl-2-ethylhexyl phosphite, hydroxyethylenediphosphonic acid, adenosine triphosphate, adenosine phosphate, mono (2-methacryloyloxyethyl) acid phosphate, mono (2 -Acryloyloxyethyl) acid phosphate, di (2-methacryloyloxyethyl) acid phosphate, di (2-acryloyloxyethyl) acid phosphate, ethyl diethyl phosphonoacetate, ethyl acid phosphate, butyl acid phosphate, butyl pyrophosphate, butoxyethyl Acid phosphate, 2-ethylhexyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, diethylene glycol acid Dohosufeto, and (2-hydroxyethyl) methacrylate acid phosphate and the like.

As other acids, benzenesulfonic acid,
Sulfonic acids such as toluenesulfonic acid, naphthalenesulfonic acid, ethanesulfonic acid, naphtholsulfonic acid, taurine, metanilic acid, sulfanilic acid, naphthylaminesulfonic acid, sulfobenzoic acid, and sulfamic acid can also be used. The stabilizers listed above can be used alone or in combination of two or more.

The photosensitive paste composition of the present invention may further contain, if necessary, other additives such as a silicone-based or acrylic-based defoaming / leveling agent, and a silane coupling agent for improving film adhesion. Can also be blended. Furthermore, if necessary, a known and commonly used antioxidant for preventing the conductive metal powder from being oxidized and a thermal polymerization inhibitor for improving the thermal stability during storage can be added.

In the photosensitive paste composition according to the present invention, the cationic dye (C) represented by the following general formula (1) and the organic boron compound (D) represented by the following general formula (2) are used in combination. Then, the cationic dye is decomposed by visible light or near-infrared light, the color of the cationic dye is erased, radicals are generated, and polymerization of the photopolymerizable component is started. Formula ^{(1): D + · A} - ( wherein, D ⁺ is a cation having an absorption in the desired wavelength region of from visible light to near infrared light, A ^- represents various anions.) General formula (2):

Embedded image (Wherein, R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group, a silyl group, a heterocyclic group, an alicyclic group or a halogen atom;
⁺ Indicates a cation. )

The decoloring reaction of the cationic dye (C) is an irreversible reaction, and the color of the cationic dye does not impair the hue of the polymer. The cationic dye of the general formula (1) may be a dye having an absorption in an arbitrary wavelength region from visible light to near infrared light, and specifically, an absorption in an arbitrary wavelength region in a range of 400 nm to 2000 nm. If there is.

The cation (D ⁺ ) of the cation dye (C) is not particularly limited as long as it has absorption in a wavelength region of 400 nm or more. Preferably,
For example, methine, polymethine, indoline, cyanine, xanthene, oxazine, thiazine, diarylmethane,
Examples include triarylmethane and cations of pyrylium-based cationic dyes.

Among such cationic dyes, representative examples of cationic dyes having absorption in the visible light region include those having cations as shown in Table 1. Representative examples of cationic dyes having absorption in the near infrared region include those having cations as shown in Tables 2 and 3. More specifically, the cationic dyes described in JP-A-5-59110 can be mentioned.

[0065]

[Table 1]

[0066]

[Table 2]

[0067]

[Table 3]

In Tables 1 to 3, λmax represents the maximum absorption wavelength, and Ph represents a phenyl group.

A is any anion, e.g., halide ions, perchlorate ions, PF ₆ ^{- -} [0069] A is a counter anion, SbF ₆ ^-, OH ^-, sulfonic acid ion, B
Four-coordinate boron anions similar to the anion part of F ₄ ⁻ or the organoboron compound of the general formula (2) are exemplified, and four-coordinate boron anions are particularly preferable.

In the general formula (2), R ¹ , R ² , R ³ , R ⁴
The alkyl group of may have a substituent, specifically, a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms is preferable, for example, a methyl group, an ethyl group,
Propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, dodecyl, cyanomethyl, 4-chlorobutyl, 2-diethylaminoethyl, methoxyethyl And the like.

In the general formula (2), R ¹ , R ² , R ³ , R ⁴
May have a substituent. Specifically, the aryl group is a substituted or unsubstituted aryl group, for example, phenyl, tolyl, xyl, mesityl, 4-methylphenyl, 2-methyl Phenyl group, 4-tert-butylphenyl group, naphthyl group, anthryl group, phenanthryl group, 4-nitrophenyl group, 4-trifluoromethylphenyl group, 4-fluorophenyl group, 4-chlorophenyl group, 4-dimethylaminophenyl And the like.

In the general formula (2), R ¹ , R ² , R ³ , R ⁴
May have a substituent. Specifically, the aralkyl group is a substituted or unsubstituted aralkyl group, for example, benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 4-methoxy A benzyl group and the like can be mentioned. The alkenyl group of R ¹ , R ² , R ³ and R ^{4 in} the general formula (2) may have a substituent. Specifically, the alkenyl group is a substituted or unsubstituted alkenyl group, for example, a vinyl group, Examples thereof include a propenyl group, a butenyl group, and an octenyl group. R ¹ , R ² , R ³ in the general formula (2)
The heterocyclic group represented by R ⁴ may have a substituent, and is specifically a substituted or unsubstituted heterocyclic group, such as a pyridyl group, a 4-methylpyridyl group, a quinolyl group, and an indolyl group. be able to.

In the general formula (2), R ¹ , R ² , R ³ , R ⁴
Alicyclic group may have a substituent, specifically a substituted or unsubstituted alicyclic group, for example, cyclohexyl group, 4-methylcyclohexyl group, cyclopentyl group,
Examples include a cycloheptyl group. The silyl group of R ¹ , R ² , R ³ , and R ^{4 in} the general formula (2) may have a substituent, and is specifically a substituted or unsubstituted silyl group, for example, a trimethylsilyl group, Examples thereof include a dimethylphenylsilyl group, a dibutylphenylsilyl group, and a triphenylsilyl group. Examples of the halogen atom of R ¹ , R ² , R ³ , and R ^{4 in} the general formula (2) include a fluorine atom and a chlorine atom.

The organic boron compound of the general formula (2)
Specific examples of the coordinated boron anion include n-butyltriphenylboron, n-octyltriphenylboron, triphenylsilyltriphenylboron, n-butyltrianisylboron, n-butyltri (p- Fluorophenyl) boron ion, n-
Butyl tri (p-trifluoromethylphenyl) boron ion, n-butyl trinaphthyl boron ion, n-butyl tri (4-methyl naphthyl) boron ion, di-n
-Dodecyldiphenyl boron ion, tetraphenyl boron ion, triphenylnaphthyl boron ion, tetrabutyl boron ion, tri-n-butyl (dimethylphenylsilyl) boron ion, and the like. Examples include anions described in the gazette.

The cation (Z ⁺ ) in the general formula (2)
Is a quaternary ammonium cation, a quaternary pyridinium cation, a quaternary quinolinium cation, a diazonium cation, a tetrazolium cation, a phosphonium cation,
(Oxo) sulfonium cations, metal cations such as sodium, potassium, lithium, magnesium and calcium; organic oxygen cations such as flavylium and pyranium salts; carbon cations such as tropylium and cyclopropylium; halogenium cations such as iodonium , Arsenic, cobalt, palladium, chromium, titanium, tin, cations of metal compounds such as antimony and the like,
Specific examples include cations described in JP-A-6-75374. These cationic dyes and organic boron compounds can be used alone or in combination of two or more.

The amount of the cationic dye (C) represented by the general formula (1) and the amount of the organoboron compound (D) represented by the general formula (2) are 0.1 to 100 parts by weight of the photosensitive component in the paste. An appropriate amount is from 01 to 20 parts by weight. 0.01
When the amount is less than 10 parts by weight, the curing does not proceed sufficiently. On the other hand, when the amount is more than 20 parts by weight, the radical generation amount becomes too large, and uneven curing is likely to occur in the photocuring (exposure) step. Become. The compounding ratio of the cationic dye (C) represented by the general formula (1) and the organic boron compound (D) represented by the general formula (2) is D / C =
It is desirable to set in the range of 0.01 to 100, preferably in the range of 0.05 to 50, and more preferably in the range of 1 to 20.

The dispersant (E) used as a paste agent in the composition of the present invention is used for forming a paste without using an organic solvent when the composition is formed into a paste. Type photosensitive paste composition,
In particular, a solventless photosensitive glass paste composition is made possible. As the dispersant (E), a carboxyl group, a hydroxyl group,
Compounds or polymer compounds having a polar group having an affinity for glass fine particles such as acid esters, for example, acid-containing compounds such as phosphates, copolymers containing acid groups, hydroxyl-containing polycarboxylic acid esters, and long chains A salt of polyaminoamide and an acid ester can be used. Among the commercially available dispersants which can be particularly preferably used, Disperbyk (registered trademark) -101, -103, -1
10, and -111 (all manufactured by Big Chemie). An appropriate amount of such a dispersant (E) is 0 to 5 parts by weight per 100 parts by weight of the inorganic fine particles (A). When the dispersant (E) is not blended, it becomes difficult to paste the composition unless an organic solvent is used. On the other hand, if the dispersant is blended in an excessive amount beyond the above range, it causes a cost increase. It is not preferable.

Next, an example of a pattern forming method using the photosensitive paste composition according to the present invention will be described. First, a method of forming a partition pattern by a lift-off method using a photosensitive paste composition will be described with reference to FIG. FIG. 2 (A)
And (B), a photosensitive film 12 is laminated on a transparent substrate 11 (generally, a glass substrate) serving as a back plate of the PDP, and a groove 13 having a predetermined pattern is formed by a photographic method. The method may be the same as the conventional method. First, as shown in FIG. 2A, after a photosensitive film 12 is attached to the surface of a transparent substrate 11, a photomask 14 having a predetermined patterned through-hole portion 15 is overlaid. After that, exposure and development are performed, and as shown in FIG. 2B, a portion of the photosensitive film that has not been exposed through a photomask is removed. When a transparent substrate having a predetermined pattern of electrodes formed on the substrate surface is used, the photomask is overlaid on the photosensitive film so that the pattern-shaped through holes of the photomask are aligned with the positions of the electrodes.

Next, as shown in FIG. 2C, the photosensitive paste of the present invention having the above-described composition was formed in a groove 13 between the patterns of the photosensitive film 12 formed by the above-described exposure and development by an appropriate method. The composition 16 is applied so as to be embedded, and is preferably defoamed under reduced pressure, and is then exposed to light and cured. Exposure light sources include low-pressure mercury lamp, medium-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, halogen lamp, argon ion laser, helium cadmium laser, helium neon laser, and krypton ion laser. Various semiconductor lasers, YAG lasers, light emitting diodes, and the like can be used. Then, the hardened glass paste surface is polished until the photosensitive film 12 becomes visible (FIG. 2D).

The substrate 11 obtained in this manner is used as a release agent in an aqueous alkaline solution, for example, at 40 ° C., 3 to 5% Na.
After immersion in a release agent solution for about 15 to 20 minutes using an OH aqueous solution or a 10 wt% aqueous monoethanolamine solution,
By immersion in water at about 0 ° C. for several tens of seconds, the photosensitive film 12 immediately swells and peels off. As shown in FIG. 2E, the substrate 11 from which the photosensitive film 12 has been peeled off is washed and dried, and then the cured glass paste is heated at a temperature of about 380 ° C. to 600 ° C. in, for example, air or a nitrogen atmosphere. Bake. Also, at this time, it is preferable to include a step of heating to about 300 ° C. to 500 ° C. and maintaining the temperature at that temperature for a predetermined time to remove the organic component as a step before the firing step.

According to such a process, the width is 30 to 100 μm.
m, a high-precision PDP partition pattern 16a having a height of about 100 to 200 μm and a uniform height without disturbance is obtained. In addition, as a material of the film which is laminated on the substrate to form the groove of the predetermined pattern, a liquid development type photosensitive resist can be used in addition to a photosensitive film (dry film). As the material of the film, a material which can be easily peeled off with an aqueous alkali solution even after the photo-curing of the photosensitive paste composition is suitably used.

In the above-described method, the method of removing the photosensitive film with a chemical (release agent) has been described. Alternatively, a method of burning off the photosensitive film at the same time as firing the glass paste is also possible. . However, in the case of the method in which the photosensitive film is also removed by baking at the same time as firing the glass paste, there is a risk that the burnt residue of the photosensitive film remains between the partition walls and black spots appear on the image. Is greatly reduced. Therefore, as a method of removing the photosensitive film,
As described above, a method using a release agent is preferable.

Next, a method of forming a fired product pattern by photolithography using an alkali-developable photosensitive paste composition will be described with reference to FIG. First, FIG.
As shown in (A), an alkali-developable photosensitive paste composition is applied to a transparent substrate 11, for example, a glass plate serving as a front substrate of a PDP, by an appropriate application method such as screen printing, a bar coater, and a blade coater. When a solvent is used in the composition, for example, about 60 to 120 ° C. in a hot-air circulation drying oven, a far-infrared drying oven or the like in order to obtain dryness to the touch.
For about 5 to 40 minutes to evaporate the organic solvent to form a tack-free film 17. Then, FIG.
As shown in FIG. 3, a photomask 14 having a predetermined exposure pattern is superimposed on the film, and selectively exposed and developed to form a film 17 having a predetermined pattern (FIG. 3).
(C)). Next, firing is performed to form a predetermined fired product pattern 17a as shown in FIG.

As the exposure step, contact exposure and non-contact exposure using a negative mask having a predetermined exposure pattern are possible, but contact exposure is preferred from the viewpoint of resolution. 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 and the like can be used.

As the developing step, a spray method, an immersion method or the like is used. Examples of the developer include aqueous solutions of metal alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium silicate; and aqueous solutions of amines such as monoethanolamine, diethanolamine, and triethanolamine, and particularly about 1.5% by weight or less. A dilute aqueous alkali solution having a concentration of is preferably used, as long as the carboxyl group of the carboxyl group-containing resin in the composition is saponified and the uncured portion (unexposed portion) is removed. However, the present invention is not limited to this. Further, it is preferable to wash with water or neutralize acid to remove unnecessary developer after development.

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

[0087]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but it is needless to say that the present invention is not limited to the following examples. Note that “parts” and “%” are based on weight unless otherwise specified.

Preparation of photosensitive paste composition: The composition was mixed at the following composition ratio, stirred by a stirrer, and then kneaded with a three-roll mill to form a paste. In addition, PbO 60%, B ₂ O ₃ 20%, S
A glass frit having a composition of 15% iO _{2 and} 5% Al ₂ O ₃ is pulverized and has a coefficient of linear expansion α ₃₀₀ = 70 × 10 ⁻⁷ / ° C., a glass transition point of 445 ° C., and an average particle size of 1.6 μm. did.

Composition Example 1 Glass fine particles 83.3 parts Alumina 12.5 parts Titanium oxide 4.2 parts Copolymerized oligoacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Ruler M101; acrylic of methacrylate copolymer Acid adduct) 2.0 parts Diethylene glycol dimethacrylate 15.0 parts Cationic dye (No. 3 in Table 1, anion is n-butyltriphenyl boron anion) 0.05 part Organic boron compound (tetrabutylammonium / n- Butyltriphenylboron) 2.0 parts Dispersant (Disperbyk-101, manufactured by Big Chemie) 0.5 part

Composition Example 2 Glass particles 83.3 parts Alumina 12.5 parts Titanium oxide 4.2 parts Copolymerized oligoacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Ruler M101) 2.0 parts Diethylene glycol dimethacrylate 15. 0 parts Cationic dye (No. 3, Table 2; anion is p-toluenesulfonic acid anion) 0.05 parts Organic boron compound (tetrabutyl ammonium / n-butyl trinaphthyl boron) 2.0 parts Dispersant (Vic Disperbyk-101, Chemie, 0.5 part

Comparative Composition Example 1 Glass fine particles 83.3 parts Alumina 12.5 parts Titanium oxide 4.2 parts Copolymerized oligoacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., ruler M101) 2.0 parts Diethylene glycol dimethacrylate 15 2.0 parts 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one 2.0 parts Dispersant (Disperbyk-101, manufactured by BYK Chemie) 0.5 part

Composition Examples 1 and 2 and Comparative Composition Example 1
Paste a photosensitive dry film on a glass substrate
Height 170 formed by forming a predetermined pattern by a true method
μm, 55μm wide groove using a squeegee
Was applied. Then, the glass paste composition
The glass substrate coated with the object is placed on a metal halide lamp (H
MW-680GW, 7kW)
Light intensity is 140mJ / cm ^TwoExposure to become glass
The paste was cured. Then the cured paste surface
After polishing until the dry film becomes visible,
This glass substrate was placed in a 5% NaOH aqueous solution at 40 ° C. for 15 minutes.
Immediately after immersion, lift and then immerse in 40 ° C water
The dry film peeled off. Removed dry film
The glass substrate was lightly washed with water. Like this glass pace
After forming a cured product, bake it in air using an electric furnace.
Was. The firing is performed at a rate of 10 ° C./min from room temperature to 450 ° C.
The temperature was raised at a temperature rate and held for 30 minutes, and then 10 ° C./min.
At a heating rate of 525 ° C., and hold for 30 minutes for baking.
And then allowed to cool to room temperature.

Preparation of alkali-developable photosensitive paste composition: Synthesis example: In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, methyl methacrylate and methacrylic acid were added in an amount of 0.76: 0.24. Charged in a molar ratio, dipropylene glycol monomethyl ether as a solvent and azobisisobutyronitrile as a catalyst were added, and the mixture was stirred at 80 ° C. for 2 to 6 hours under a nitrogen atmosphere to obtain a resin solution. The resin solution was cooled, and methylhydroquinone was used as a polymerization inhibitor, tetrabutylphosphonium bromide was used as a catalyst, and glycidyl methacrylate was added at 95 to 105 ° C for 16 hours under the conditions of 0.12 to 1 mol of carboxyl groups of the resin. The addition reaction is performed at an addition molar ratio of a molar ratio,
Removed after cooling. The resin A produced by the above reaction has a weight average molecular weight of about 10,000 and an acid value of 59 mg KOH.
/ G, double bond equivalent was 950. The weight average molecular weight of the obtained copolymer resin was measured by using a pump LC-6AD manufactured by Shimadzu Corporation and a column Sh manufactured by Showa Denko KK
odex (registered trademark) KF-804, KF-803, K
The measurement was performed by high performance liquid chromatography in which three F-802s were connected.

The resin A obtained in the above synthesis example was blended at the following composition ratio, stirred by a stirrer, and then kneaded with a three-roll mill to form a paste. In addition, PbO 60%, B ₂ O ₃
A glass frit having a composition of 20%, SiO ₂ 15% and Al ₂ O ₃ 5% is pulverized, and has a coefficient of linear expansion α ₃₀₀ = 70 × 10 ^−7.
/ ° C, a glass transition point of 445 ° C, and an average particle size of 1.6 µm.

Composition Example 3 Resin A 100.0 parts Pentaerythritol triacrylate 50.0 parts Dipropylene glycol monomethyl ether 80.0 parts Black pigment 150.0 parts Glass fine particles 500.0 parts Cationic dye (No. in Table 1) 3. Anion is n-butyltriphenylboron anion) 0.25 parts Organic boron compound (tetrabutylammonium / n-butyltriphenylboron) 10.0 parts

Composition Example 4 Resin A 100.0 parts Pentaerythritol triacrylate 50.0 parts Dipropylene glycol monomethyl ether 80.0 parts Black pigment 150.0 parts Glass fine particles 500.0 parts Cationic dye (No. in Table 2) 3. Anion is p-toluenesulfonic acid anion) 0.25 parts Organic boron compound (tetrabutyl ammonium / n-butyl trinaphthyl boron) 10.0 parts

Composition Example 5 Resin A 100.0 parts Pentaerythritol triacrylate 50.0 parts Dipropylene glycol monomethyl ether 80.0 parts Silver powder 450.0 parts Glass fine particles 22.0 parts Cationic dye (No. 3 in Table 1) , Anion is n-butyltriphenylboron anion) 0.1 part Organic boron compound (tetrabutylammonium / n-butyltriphenylboron) 5.0 parts

Composition Example 6 Resin A 100.0 parts Pentaerythritol triacrylate 50.0 parts Dipropylene glycol monomethyl ether 80.0 parts Silver powder 450.0 parts Glass fine particles 22.0 parts Cationic dye (No. 3 in Table 2) , Anion is p-toluenesulfonic acid anion) 0.1 part Organic boron compound (tetrabutylammonium / n-butyltrinaphthylboron) 5.0 parts

Composition Example 7 Resin A 100.0 parts Pentaerythritol triacrylate 50.0 parts Dipropylene glycol monomethyl ether 80.0 parts Silver powder 150.0 parts Glass fine particles 25.0 parts Black pigment 100.0 parts Cationic dye (No. 3 in Table 1, anion is n-butyltriphenylboron anion) 0.25 parts Organic boron compound (tetrabutylammonium / n-butyltriphenylboron) 10.0 parts

Composition Example 8 Resin A 100.0 parts Pentaerythritol triacrylate 50.0 parts Dipropylene glycol monomethyl ether 80.0 parts Silver powder 150.0 parts Glass fine particles 25.0 parts Black pigment 100.0 parts Cationic dye (No. 3 in Table 2, anion is p-toluenesulfonic acid anion) 0.25 parts Organic boron compound (tetrabutyl ammonium / n-butyl trinaphthyl boron) 10.0 parts

Comparative Composition Example 2 Resin A 100.0 parts Pentaerythritol triacrylate 50.0 parts Dipropylene glycol monomethyl ether 80.0 parts Black pigment 150.0 parts Glass fine particles 500.0 parts 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) -butan-1-one 10.0 parts

Comparative Composition Example 3 Resin A 100.0 parts Pentaerythritol triacrylate 50.0 parts Dipropylene glycol monomethyl ether 80.0 parts Silver powder 450.0 parts Glass fine particles 22.0 parts 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) -butan-1-one 5.0 parts

Comparative Composition Example 4 Resin A 100.0 parts Pentaerythritol triacrylate 50.0 parts Dipropylene glycol monomethyl ether 80.0 parts Silver powder 150.0 parts Glass fine particles 25.0 parts Black pigment 100.0 parts 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one 10.0 parts

Composition Examples 3 to 8 and Comparative Composition Examples 2
4 was applied to the entire surface of a glass substrate using a 300-mesh polyester screen. Next, the film was dried at 90 ° C. for 20 minutes using a hot air circulation type drying furnace to form a film having good dryness to the touch. Then, the line width 100μ
Using a negative film of a stripe pattern having a space width of 100 μm and a metal halide lamp as a light source, exposure was performed so that the integrated amount of light on the composition was 500 mJ / cm ² . Thereafter, 1 wt% Na _{2 at} a liquid temperature of 30 ° C.
Development was carried out using a CO ₃ aqueous solution, followed by washing with water. Finally, it was fired in air using an electric furnace. In the firing, the temperature was raised from room temperature to 450 ° C. at a rate of 5 ° C./min.
At 30 ° C. for 30 minutes, and then at a rate of 5 ° C./min.
A step of raising the temperature to 50 ° C., firing for 30 minutes, and then allowing to cool to room temperature was performed.

Table 4 shows the evaluation results of the respective characteristics evaluated for each of the obtained substrates.

[Table 4] The evaluation methods in Table 4 are as follows.

(1) Line shape after pattern formation The pattern of the photosensitive paste composition by the cured product after peeling off the dry film and the pattern of the alkali-developable photosensitive paste composition after development are observed with a microscope. The evaluation was made based on whether there was no irregular variation and there was no twist. The evaluation criteria are as follows. ：: There is no irregular variation, and there is no twist. Δ: Slight irregular irregularities, warping, etc. X: Irregular variation, distortion, etc. are present.

(2) Line shape after firing The line shape after firing was evaluated by observing a pattern completed up to firing with a microscope and confirming that there was no irregular variation in the lines and no deviation or the like. The evaluation criteria are as follows. ：: There is no irregular variation, and there is no twist. Δ: Slight irregular irregularities, warping, etc. X: Irregular variation, distortion, etc. are present.

(3) Adhesion The adhesion was evaluated by peeling with a cellophane pressure-sensitive adhesive tape and checking for peeling of the pattern. The evaluation criteria are as follows. ：: There is no peeling of the pattern. Δ: There is slight peeling of the pattern. X: The pattern is often peeled.

(4) Curling of Pattern Edge The curling of the pattern edge was evaluated by measuring the surface roughness of the pattern edge with a surface roughness meter. The evaluation criteria are as follows. ：: Almost no edge curl. Δ: Slight edge curl. X: The edge curl is severe.

[0110]

As described above, the photosensitive paste composition of the present invention is excellent in photocurability and resolution, and particularly exhibits excellent photocuring depth. Can be improved. Therefore, warpage and line width shrinkage during firing are unlikely to occur, and high aspect ratio and high precision pattern processing becomes possible. Further, when the film thickness is the same, the minimum exposure amount that can form the same line / space pattern can be reduced, and energy saving can be realized. Therefore, in manufacturing a plasma display panel, a fired pattern such as a partition pattern, an electrode pattern, a dielectric pattern, and a black matrix pattern having a high aspect ratio and high accuracy 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.

FIG. 2 is a schematic process explanatory view of a method for forming a fired product pattern by a lift-off method.

FIG. 3 is a schematic process explanatory view of a fired product pattern forming method by photolithography.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Front glass substrate 2a, 2b Display electrode 3a, 3b Transparent electrode 4a, 4b Bus electrode 5 Dielectric layer 6 Protective layer 7 Back glass substrate 8 Rib 9 Address electrode 10a, 10b, 10C Phosphor film 11 Transparent substrate 16 Photosensitive paste Composition 16a Partition pattern 17 Coating 17a Fired pattern

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) H01J 11/02 H01J 11/02 B (72) Inventor Mayumi Akakawa Okura 388, Okura, Arashiyama-cho, Hiki-gun, Saitama (72) Inventor Seiya Onodera Seiya Onodera, Arashiyama-cho, Higashi-gun, Saitama Prefecture 388, Okura, Taiyo Ink Manufacturing Co., Ltd. (72) Inventor Katsumi Murobushi No. 5, Ogimachi, Kawasaki-ku, Kawasaki-shi No. 1 In Showa Denko KK, Kawasaki Research Laboratory (72) Inventor Morihiko Yamada 1-13-9 Shiba-Daimon, Minato-ku, Tokyo F-term in Showa Denko KK (reference) 2H025 AA02 AA03 AB15 AB17 AC01 AC08 AD01 BC12 BC14 BC31 BC34 BC43 BC51 BC81 BC85 BC92 CA39 CA41 CA42 CC04 CC08 CC09 CC12 CC20 DA20 FA17 FA28 2H096 AA26 AA27 BA05 EA02 EA04 GA08 H A01 4J011 AC04 PA04 PA05 PA07 PA13 PA14 PA15 PA28 PA48 PA53 PA54 PA64 PA65 PA67 PA69 PB22 PB25 PB27 PB40 QA02 QA03 QA04 QA06 QA08 QA09 QA13 QA19 QA22 QA23 QA24 QA26 QA32 QA33 QA37 QAQA QB QA QA QA QB QA QA QA QA QA QA QA QA QA Q RA10 RA11 SA01 SA21 SA22 SA31 SA32 SA51 SA63 SA64 SA76 SA78 SA82 SA84 SA85 SA86 SA87 SA88 SA89 TA03 TA06 TA07 TA08 UA01 UA06 VA01 WA01 5C040 GC18 GD07 GF18 GH07 KA01 KA04 KA09 KA16 KB03 KB11 KB17 KB19 DA10 DA26 DA26 MA26 DA11 DA12 DA23 DA34 DA42 DD01

Claims (9)

[Claims] 1. An inorganic component, (B) an organic component containing a photopolymerizable compound, (C) a cationic dye represented by the following general formula (1), and (D) a cationic dye represented by the following general formula (2). A photosensitive paste composition comprising an organic boron compound represented by the formula: Formula ^{(1): D + · A} - ( wherein, D ⁺ is a cation having an absorption in the desired wavelength region of from visible light to near infrared light, A ^- represents various anions.) General formula (2): (Wherein, R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group, a silyl group, a heterocyclic group, an alicyclic group or a halogen atom;
⁺ Indicates a cation. ) 2. The method according to claim 1, wherein the inorganic fine particles (A) are glass fine particles,
1 of inorganic filler, pigment, conductive metal powder or metal oxide
The photosensitive paste composition according to claim 1, wherein the composition comprises at least one species. 3. The method according to claim 1, wherein the glass particles have a glass transition point (T
g) 300-500 ° C, glass softening point (Ts) 400-
The photosensitive paste composition according to claim 2, which has a temperature of 600 ° C. 4. The method according to claim 1, wherein the conductive metal powder is Ag, Au, Pd,
The photosensitive paste composition according to claim 2, wherein the photosensitive paste composition is at least one kind of metal powder or metal oxide selected from the group consisting of Ni, Cu, Al, and Pt and is contained in a photosensitive conductive paste. 5. The organic component (B) containing the photopolymerizable compound contains a photosensitive monomer, oligomer and / or polymer having at least one (meth) acryloyl group in one molecule. The photosensitive paste composition according to claim 1. 6. The organic component (B) containing the photopolymerizable compound has a carboxyl group-containing weight average molecular weight of 1,
000-100,000 and acid value 20-150mgKO
The photosensitive paste composition according to any one of claims 1 to 5, comprising an H / g oligomer or polymer and being formed in an alkaline development type. 7. The organic component (B) containing the photopolymerizable compound has a weight average molecular weight of 1,000 to 100,000 having a carboxyl group and an ethylenically unsaturated group, and an acid value of 2.
0 to 150 mgKOH / g, and its double bond equivalent is 3
The photosensitive paste composition according to any one of claims 1 to 6, comprising 50 to 2,000 oligomers or polymers, and being formed in an alkaline development type. 8. The photosensitive paste composition according to claim 1, further comprising (E) a dispersant having a polar group having an affinity for glass fine particles. 9. The photosensitive paste composition according to claim 1, which is selected from the group consisting of a partition pattern, a dielectric pattern, an electrode pattern, and a black matrix pattern of a plasma display panel. A panel on which at least one kind of fired product pattern is formed.