JP2000298344A - Positive photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the alkali-developable positive photosensitive composition superior in storage stability (viscosity stability) even in the case of containing an extremely large amount of an inorganic powder such as a glass powder, exhibiting high resolution without causing undercut and capable of easily forming a highly precise image in a large area by a photolithographic technology. SOLUTION: The first fundamental embodiment of the positive photosensitive composition is (A) a polymer having a main chain having >=2 bonding groups of 1,000-100,000 weight average molecular weight and (B) a compound to be induced by irradiation with activated energy rays, and the second embodiment, in addition to them, further, (C) an inorganic powder, such as a glass powder, a ceramic powder, a black powder, or a conductive powder, and it is preferred to use polyhemiacetal ester of a dicarboxylic acid with a divinylether.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive material suitable as an etching resist, a glass paste, and a conductive paste used for manufacturing a printed wiring board, a liquid crystal display panel, and a plasma display panel (hereinafter abbreviated as PDP). Resin composition, especially PD
The present invention relates to an alkali development type positive photosensitive resin composition useful as a partition wall material, an electrode material, and a black matrix material of P.

[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, and is classified into a DC type and an AC type according to a panel structure and a driving method. The principle of the color display by the PDP is that a plasma discharge is generated in a cell space (discharge space) between two opposing electrodes formed on a front glass substrate and a rear glass substrate separated by a rib (partition wall), and each cell is discharged. The phosphor formed on the inner surface of the rear glass substrate is excited by ultraviolet rays generated by the discharge of a gas such as He or Xe sealed in the space to generate visible light of three primary colors. Therefore, each cell space is defined by lattice-shaped ribs in the DC-type PDP, and is defined by ribs arranged in parallel to the substrate surface in the AC-type PDP. Are defined by ribs.

FIG. 1 partially shows a structural example 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 large number of pairs of display electrodes 2a and 2b each having a predetermined pitch, 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. It is lined up. These display electrodes 2
A transparent dielectric layer 5 (low-melting glass) for accumulating electric charges is formed by printing and firing on a and 2b, and a protective layer (MgO) 6 is deposited thereon. 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 7, a large number of stripe-shaped ribs (partitions) 8 for dividing discharge spaces and address electrodes (data electrodes) 9 arranged in each discharge space are arranged at a predetermined pitch. Has been established. The inner surface of each discharge space has red (10a), green (10b), and blue (10c).
The color phosphor films are regularly arranged. In a full-color display, one pixel is constituted by the phosphor films 10a, 10b, and 10c of the three primary colors of red, green, and blue.

In the PDP, an AC pulse voltage is applied between the pair of display electrodes 2a and 2b to cause discharge between the electrodes on the same substrate (surface discharge method). The phosphor films 10a and 10 of the substrate 7
b, 10c are excited, and visible light generated is seen through the transparent electrodes 3a, 3b of the front substrate 1 (reflection type).

In a PDP having such a structure,
As a method of forming the partition, a method of patterning a glass paste by a screen printing method is known. However, the method of forming a partition pattern by the screen printing method requires skill, and has problems such as blurring and bleeding during printing, a decrease in alignment accuracy due to expansion and contraction of the screen, and a low yield. It has become difficult to deal with large screens and high definition.

On the other hand, a photolithography method has been conventionally proposed as a method of forming a partition pattern which can be substituted for the screen printing method (for example, Japanese Patent Application Laid-Open No. 1-29-1990).
6534, JP-A-2-165538, JP-A-5-3
No. 42992). In this photolithography method, a substrate is coated with an ultraviolet-curable glass paste material, and a pattern is formed by exposure and development. As the UV-curable glass paste material used in the photolithography method, an alkali-developable glass paste material is advantageous, and in particular, a polymer compound having both a carboxyl group and an unsaturated double bond, or a functional group containing these compounds separately. A negative-type photosensitive glass paste obtained by adding a polymer, a monomer, and the like to a glass paste together with a photopolymerization initiator is generally known.

However, the negative type photosensitive glass paste has a problem of viscosity stability that the viscosity increases in a short time because the basic glass powder and the polymer compound having a carboxyl group are mixed. On the other hand, recently, a method of adding an organic acid or an inorganic acid has been proposed in order to prevent the paste from thickening.

However, in any case, since an acidic component is added to the paste in addition to the polymer compound having a carboxyl group, there is a disadvantage that the development resistance of the photocured portion tends to decrease during alkali development. In particular, in the case of a negative photosensitive glass paste, since a large amount of glass powder or the like is contained in the components, the contact portion between the substrate and the paste is insufficiently exposed, and is insufficiently cured. Undercuts were easily generated, and there was a limit in forming a fine pattern.

On the other hand, for the purpose of forming a fine pattern, it is conceivable to use a positive photosensitive resin composition known as an etching resist for a photosensitive glass paste. However, the conventional positive-type photosensitive resin composition generally contains a photosensitive resin having a naphthoquinone-based resin skeleton, so that a residue easily remains after firing, and is not applied to the formation of a fired product pattern. Is the fact.
In addition, this positive type photosensitive resin composition certainly satisfies the characteristics as an etching resist, but has the disadvantage that the sensitivity is insufficient and the resist must be removed with a strong basic solution. there were.

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems and disadvantages of the prior art. Alkali-developing type that has excellent storage stability (viscosity stability) even when it contains, shows high resolution without undercut, and can easily form large area high-definition patterns by photolithography technology. To provide a photosensitive resin composition of the present invention. Another object of the present invention is to provide a positive photosensitive resin composition which has excellent sensitivity and is useful as an etching resist which can be peeled and removed even by a weak alkaline aqueous solution by irradiating ultraviolet rays. It is in.

[0012]

Means for Solving the Problems In order to achieve the above object, a first basic mode of the positive photosensitive resin composition according to the present invention comprises (A) a main chain represented by the following general formula (1): Having a weight average molecular weight of 1,000 or more having two or more linking groups represented by
100,000 polymer, and (B) a compound capable of generating an acid upon irradiation with active energy rays (hereinafter referred to as a photoacid generator). Weight average molecular weight of 1,000 to 10 having two or more linking groups represented by the following general formula (1) in the main chain.
000 polymers, (B) a photoacid generator, and (C) an inorganic powder.

Embedded image

The inorganic powder includes (C-1)
At least one inorganic powder selected from glass powder, (C-2) ceramic powder, (C-3) black pigment, and (C-4) conductive powder is preferably used. Further, the polymer (A) is a polymer of dicarboxylic acid and divinyl ether and has a weight average molecular weight of about 1,000 to 100,000.
A polyhemiacetal ester of 00 is preferably used. Further, such a positive photosensitive resin composition of the present invention may be in the form of a paste or in the form of a dry film previously formed into a film.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The positive photosensitive resin composition of the present invention has, as an essential component, a weight average molecular weight of 1,000 or more having two or more linking groups represented by the above general formula (1) in the main chain.
It is characterized in that it contains Ａ100,000 of polymer (A), preferably a polyhemiacetal ester obtained from a polyaddition reaction between a dicarboxylic acid and a divinyl ether compound. Thereby, the positive photosensitive resin composition of the present invention,
Since the film-forming component is composed of a resin with a carboxyl group incorporated into the main chain link, it has excellent storage stability (viscosity stability) even if it contains an extremely large amount of inorganic fine powder such as glass powder. It will be. Moreover, since the positive photosensitive resin composition of the present invention is a positive photosensitive resin composition using a main chain-cutting type polyhemiacetal ester and a photoacid generator, it has excellent sensitivity, It is possible to form a high-definition pattern with high resolution without cutting.

According to the positive photosensitive resin composition of the present invention, the photoacid generator (B) is decomposed by irradiation with active energy rays, preferably ultraviolet rays, to generate an acid. The main chain of the polymer (A) is cleaved by a catalytic action to generate a free carboxyl group, so that the polymer (A) becomes soluble in an aqueous alkali solution. Therefore, the exposed portion of the etching resist formed using such a composition can be easily removed and removed with an alkaline aqueous solution. That is, the resist can be stripped and removed with the same solution as the developing solution (for example, a weak alkaline aqueous solution such as sodium carbonate) used for forming the pattern of the etching resist, and the process can be simplified. That is, there is a feature that development, peeling, and removal can be performed with the same solution in all steps.

In the positive photosensitive resin composition of the present invention, the polymer (A) constituting the film-forming component
Is limited to the range of 1,000 to 100,000. The reason is that the weight average molecular weight is 1,0.
If it is less than 00, the strength of the dried coating film becomes weak and peeling or the like tends to occur during development. On the other hand, if it exceeds 100,000, development with a weak alkaline aqueous solution may become difficult, which is not preferable.

In the composition of the present invention, a polyhemiacetal ester particularly suitable as the polymer (A) is a compound having two carboxyl groups and a compound having two vinyl ether groups. In the presence of
It is synthesized by reacting at room temperature to 100 ° C. Although this synthesis reaction proceeds even without a catalyst, it is preferable to use a trace amount of an acid catalyst as necessary. Here, as the compound having two carboxyl groups, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
Examples include dicarboxylic acids such as azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, and cyclohexanedicarboxylic acid.Bifunctional carboxylic acid compounds obtained by adding an acid anhydride to a diol such as neopentylglycol can also be used. . Compounds having two vinyl ether groups include, for example, butanediol divinyl ether, cyclohexanediol divinyl ether, cyclohexane dimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, ethylene glycol divinyl ether And divinyl ether compounds such as hexanediol divinyl ether.

The polyhemiacetal ester thus synthesized preferably has an acid value derived from the carboxyl group remaining at the terminal of the main chain of less than 15 mgKOH / g. The reason is that when the acid value is 15 mgKOH / g or more,
The reason for this is that the non-irradiated portion of the coating film on the non-irradiated portion with the active energy ray has insufficient developing resistance to a weak alkaline aqueous solution, and it is difficult to form a good pattern, which is not preferable. In particular, since the free carboxyl group acts as a decomposition catalyst during heating or inhibits the stability of the glass paste, the acid value of the resin is 10
It is more preferable that the content be not more than mgKOH / g. The residual carboxyl group may be blocked with a monovinyl ether compound after the synthesis of the resin.

The polymer (A) is used in an amount of 5 to 5 based on the total amount of the composition.
It is preferable to mix at a ratio of 0% by weight. If the amount of the polymer is too small than the above range, the distribution of the resin in the film to be formed is likely to be uneven, selective exposure,
It becomes difficult to form a high-definition pattern by development. on the other hand,
If the amount is more than the above range, the pattern is likely to be distorted during firing and line width shrinkage is likely to occur.

The positive photosensitive resin composition of the present invention contains, as an essential component, a photoacid generator, ie, a compound (B) which generates an acid upon irradiation with an active energy ray, in addition to the polymer (A). . Examples of the photoacid generator (B) include various cationic polymerization initiators, for example, onium salts such as diazonium salts, iodonium salts, bromonium salts, chloronium salts, sulfonium salts, selenonium salts, pyrylium salts, thiapyrylium salts, and pyridinium salts; Halogenated compounds such as (trihalomethyl) -s-triazine and derivatives thereof; 2-nitrobenzyl ester of sulfonic acid;
1-oxo-2-diazonaphthoquinone-4-sulfonate derivative; N-hydroxyimide = sulfonate; tri (methanesulfonyloxy) benzene derivative; bissulfonyldiazomethanes; sulfonylcarbonylalkanes; sulfonylcarbonyldiazomethanes; disulfone Compounds and the like are used.

These photoacid generators (B) can be used alone or in combination of two or more. Examples of commercially available products include CYRACURE (registered trademark) UVI-6950, manufactured by Union Carbide Co., Ltd.
VI-6970, Optomer SP-1 manufactured by Asahi Denka Kogyo Co., Ltd.
50, SP-151, SP-152, SP-170, S
Examples thereof include triarylsulfonium salts, unsubstituted or substituted aryldiazonium salts, and diaryliodonium salts such as P-171, CI-2855 manufactured by Nippon Soda Co., and Degacere KI 85 B manufactured by Degussa Corporation.
As a sulfonic acid derivative, PAI manufactured by Midori Kagaku
-101 and the like.

The above-mentioned photoacid generator (B) is preferably blended at a ratio of 1 to 40 parts by weight based on 100 parts by weight of the polymer (A). The reason for this is that if the amount of the photoacid generator (B) is too small, the development residue tends to occur, making it difficult to form a fine pattern. On the other hand, if the amount is larger than the above range, unexposed portions are peeled off by halation, which is not preferable.

When the positive photosensitive resin composition of the present invention is used as a glass paste or a conductive paste, an inorganic powder (C) according to the intended use is blended to form a paste.
That is, the positive photosensitive resin composition of the present invention contains (C-1) glass powder, (C-2) ceramic powder,
(C-3) Black pigment and (C-4) conductive powder can be blended.

For example, as the glass powder (C-1) used when formulating the composition of the present invention as a glass paste, a low-melting glass powder having a softening point of 300 to 600 ° C. is used, and lead oxide and bismuth oxide are used. Alternatively, those containing zinc oxide as a main component can be suitably used. As the low melting point glass powder, those having a glass transition temperature of ₃₀₀ to 580 ° C. and a coefficient of thermal expansion α ₃₀₀ of 70 to 90 × 10 ⁻⁷ / ° C. are preferably used.
It is desirable to use one having a thickness of 5 μm or less. Further, the amount of the glass powder to be blended is suitably from 25 to 1,000 parts by weight per 100 parts by weight of the polymer (A).

Preferable examples of the glass powder containing lead oxide as a main component include PbO of 48 to 100% by weight on an oxide basis.
82%, B ₂ O 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. Note that, in addition to the above glass components, glass containing lithium, fluorine, and phosphorus can be used.

As the ceramic powder (C-2), one or more of alumina, cordierite and zircon can be used. This ceramic powder has an average particle size of 10 μm or less, preferably 2.5 μm, from the viewpoint of resolution.
It is desirable to use one of μm or less. Further, the ceramic powder can be blended at a ratio of 1 to 100 parts by weight based on 100 parts by weight of the glass powder (C-1).

As the black pigment (C-3) used when the color tone of the paste is made black, inorganic pigments having excellent heat resistance can be widely used. Generally, Cu, Fe,
Oxides such as Cr, Mn, Co, Ni, and Ru, composite oxides, and lanthanum borates (LaB ₆ ) correspond thereto, and these can be used alone or in combination of two or more. The average particle size of the black pigment (C-3) is preferably 20 μm or less, and more preferably 5 μm or less from the viewpoint of resolution. The amount of the black pigment is 1 to 100 parts by weight of the glass powder (C-1).
It is preferred to mix at a ratio of 100 parts by weight.

The conductive powder (C-4) used when formulating the composition of the present invention as a conductive paste is widely used as long as the conductive powder has a specific resistance of 1 × 10 ³ Ω · cm or less. be able to. Specifically, silver (Ag),
Gold (Au), nickel (Ni), copper (Cu), aluminum (Al), tin (Sn), lead (Pb), zinc (Z
n), iron (Fe), platinum (Pt), iridium (I
r), osmium (Os), palladium (Pd), rhodium (Rh), ruthenium (Ru), tungsten (W), molybdenum (Mo), and other alloys, as well as tin oxide (SnO ₂ ), indium oxide ( In ₂ O ₃ ), IT
O (Indium Tin Oxide) or the like can be used.
These can be used alone or as a mixed powder of two or more types.

As the shape of the conductive powder (C-4), various shapes such as a spherical shape, a flake shape, and a dendrite shape can be used, but it is preferable to use a spherical shape in consideration of light characteristics and dispersibility. . The average particle size is preferably 20 μm or less from the viewpoint of resolution, preferably 5 μm.
It is desirable to use one of μm or less. 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. Fatty acids include oleic acid, linoleic acid, linolenic acid, stearic acid and the like. An appropriate amount of the conductive powder is 500 parts by weight or less per 100 parts by weight of the polymer (A). A large amount exceeding 500 parts by weight is not preferred because light transmission is impaired and sufficient photocurability of the composition is hardly obtained.

It is preferred that the positive photosensitive resin composition of the present invention contains a sensitizer for the purpose of sensitizing the photoacid generator (B). Examples of the sensitizer include anthracene derivatives, naphthalene derivatives, phenanthrene derivatives,
Unsaturated ketones represented by condensed polycyclic aromatic derivatives such as pyrene derivatives, naphthacene derivatives, perylene derivatives, pentacene derivatives, acridine derivatives, benzothiazole derivatives, chalcone derivatives and dibenzalacetone, benzyl and camphor-quinone 1,2-diketone derivatives, benzoin derivatives, fluorene derivatives,
Naphthoquinone derivative, anthraquinone derivative, xanthene derivative, thioxanthene derivative, xanthone derivative,
Polymethine dyes such as thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, rose bengal derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, Porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinopolyphyrazine derivative, phthalocyanine derivative, tetraazapolyphyrazine derivative, tetraquinoxalillopolyphyrazine derivative, naphthalocyanine derivative, sub Phthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, annulene derivative, Examples include, but are not limited to, pyrropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, and the like, and other dyes that absorb light in the ultraviolet to near infrared region. And sensitizers, and two or more of these may be used at any ratio as needed.

The sensitizer is preferably blended in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the polymer (A). The reason for this is that if the amount of the component deviates from the above range, it is difficult to obtain a sensitizing effect, which is not preferable.

Further, the positive photosensitive resin composition of the present invention preferably contains a diluting solvent for the purpose of facilitating the formation of a paste and enabling the coating step. The coating film thus formed can be subjected to contact exposure by a drying treatment.
Specific examples of such a diluting solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, carbitol, methyl carbitol, butyl carbitol, Glycol ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate Acetates such as propylene glycol monomethyl ether acetate; ethanol, propanol, ethylene glycol Alcohols such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha, alone or in combination of two or more. Can be used. The organic solvent can be blended in an amount that does not hinder the coatability, in a proportion that can be adjusted to a desired viscosity of the composition according to the coating method.

The positive photosensitive composition of the present invention includes:
Within the range that does not impair the desired properties, if necessary,
Silicone-based, acrylic-based antifoaming agents and leveling agents,
Other additives such as a silane coupling agent for improving the adhesion of the film can be blended. Furthermore, if necessary, organic dyes and organic pigments for preventing light scattering, and metal oxides, silicon oxides, and fine particles such as boron oxides as binding components with the substrate during firing can be added. .

The positive photosensitive resin composition of the present invention composed of the above-described components may be directly laminated on a substrate when it is formed into a film in advance. In the case of the composition, it is applied to a substrate, for example, a glass substrate serving as a front substrate of a PDP, by a suitable application method such as a screen printing method, a bar coater, and a blade coater, and then a hot-air circulating drying furnace to obtain a touch-drying property For example, drying is performed at about 60 to 120 ° C. for about 5 to 40 minutes to evaporate the diluting solvent to obtain a tack-free coating film. The heating and drying temperature at this time is desirably 70 ° C. or higher. Thereafter, after selective exposure, post-baking is performed in a hot air circulation type drying furnace or the like, and finally, development and firing are performed to form a predetermined sintered body pattern.

As the exposure step, contact exposure and non-contact exposure using a photomask 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.
Halogen lamps, high-pressure mercury lamps, laser light, metal halide lamps, black lamps, electrodeless lamps and the like are used.

The post-baking after exposure is intended to further promote the decomposition reaction of the polymer (A),
The heating temperature at this time is about 70 to 150 ° C and about 5 to 60.
For about 5-30 minutes at about 90-120 ° C.

As the developing step, a spray method or an immersion method is used. As the developer, aqueous solutions of alkali metals such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium silicate, and aqueous solutions of amines such as monoethanolamine, diethanolamine and triethanolamine are widely used. It is sufficient that the carboxyl group of the polycarboxylic acid in the composition generated by the decomposition reaction of the polymer (A) during the post-baking step is saponified and the exposed portion is removed. It is not something to be done. After the development, it is preferable to carry out washing with water or acid neutralization in order to remove an unnecessary developer.

In the firing step, the substrate after development is subjected to a heat treatment at about 450 to 600 ° C. in air or in a nitrogen atmosphere to form a desired sintered body pattern. Prior to the firing, it is preferable to set a step of removing an organic substance to be maintained at about 400 to 500 ° C. for a predetermined time.

[0041]

EXAMPLES The present invention will be specifically described below with reference to 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.

Resin Synthesis Example In a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, 32.12 parts of cyclohexanedimethanol, 14.99 parts of hexahydrophthalic anhydride, and As a solvent, 30.00 parts of a petroleum-based solvent (Solvesso # 200, manufactured by Exxon Chemical Co., Ltd.) was added.
The mixture was stirred at 140 ° C. for 4 to 6 hours. When the conversion reached 97% or more, the reaction was terminated to obtain a dicarboxylic acid compound. Next, 22.89 parts of cyclohexanedimethanol divinyl ether are added to the solution of the dicarboxylic acid compound while stirring at 110 ° C., and an addition reaction is carried out for 4 to 10 hours while maintaining the temperature at 110 ° C., so that the conversion becomes 95% or more. The reaction was completed at that point, and the reaction mixture was cooled and taken out to produce a polyhemiacetal ester solution (varnish A). This polyhemiacetal ester had a weight average molecular weight of about 10,000. The weight-average molecular weight of the resin was measured using a pump LC-6AD manufactured by Shimadzu Corporation and a column S manufactured by Showa Denko KK
hodex (registered trademark) KF-804, KF-803,
The measurement was performed by high performance liquid chromatography in which three KF-802s were connected.

Next, a synthetic example of a negative photosensitive resin will be described as a comparative example. Comparative 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 a volume of 0.1%.
Charged at a molar ratio of 76: 0.24, 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. This resin solution was cooled, and methylhydroquinone was used as a polymerization inhibitor, and tetrabutylphosphonium bromide was used as a catalyst, and glycidyl methacrylate was subjected to an addition reaction at 95 to 105 ° C for 16 hours at a molar ratio of 0.12 to carboxyl groups, After cooling, the varnish B was formed. The varnish B had a weight average molecular weight of about 10,000 and an acid value of 60 m.
gKOH / g, double bond equivalent was 950.

The varnishes A and B thus obtained were blended at the following composition ratios, stirred with a stirrer, and then kneaded with a three-roll mill to form a paste.
The glass powder used at this time was PbO
_{60%, B 2 O 3 20} %, SiO 2 15%, Al 2 O 3 5
% Glass is crushed and the coefficient of thermal expansion α ₃₀₀ = 70 ×
10 ^-7 / ° C, glass transition point 445 ° C, average particle size 2.5μ
m was used. Further, as the black pigment, a Cu, Cr, Mn-based oxide having an average particle diameter of 1 μm was used.

Example 1 100 parts of varnish A SP-152 (photoacid generator manufactured by Asahi Denka Kogyo KK) 5 parts phenothiazine 0.5 part Solvesso # 200 20 parts Glass frit 600 parts Black # 3900 (Asahi Kasei Kogyo KK) Heat resistant black pigment) 50 parts Silicone defoamer (KS-66, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part

Example 2 Varnish A 100 parts SP-152 (Asahi Denka Kogyo Co., Ltd. photoacid generator) 5 parts Phenothiazine 0.5 parts Solvesso # 200 10 parts Glass frit 20 parts Silver powder (average particle diameter 1 μm) 400 Part Silicone defoamer (KS-66, Shin-Etsu Chemical Co., Ltd.) 1 part

Comparative Example 1 Varnish B 100 parts Pentaerythritol triacrylate 50 parts 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one 15 parts Dipropion glycol monomethyl ether 100 parts Glass frit 500 parts Black # 3900 (heat-resistant black pigment manufactured by Asahi Kasei Kogyo Co., Ltd.) 50 parts Silicone defoamer (KS-66 manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part

Comparative Example 2 Varnish B 100 parts Pentaerythritol triacrylate 50 parts 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one 15 parts Dipropion glycol monomethyl ether 100 parts Glass frit 20 parts Silver powder (average particle size 1 μm) 400 parts Silicone defoamer (KS-66, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part

Examples 1 and 2 thus obtained and a comparative example
First, the storage stability of each of the paste compositions 1 and 2 was determined.
When evaluating and producing an evaluation substrate under the following conditions,
Survivability, space developability, presence or absence of undercut and
After firing and firing, the line shape was evaluated. Fabrication conditions for evaluation substrate
And the evaluation method is as follows. Production conditions: 30 parts of the above paste composition were placed on a glass substrate.
Using a 0 mesh polyester screen
Cloth and the formed coating film are heated to 80 ° C using a hot air circulation drying oven.
X 20 minutes to dry under good dry condition
did. Next, line / space = 50/50 (μm / μ
Use a mask film with a stripe pattern
The light source is a metal halide lamp and the integrated light on the coating film
700mJ / cm ^TwoExposure and hot air circulation
It was heated under the condition of 90 ° C. × 10 minutes using a drying oven.
Then, 1 wt% Na at a liquid temperature of 30 ° C._TwoCO_ThreeUsing an aqueous solution
The statue was made and washed with water. And finally 45 in the air
Baking at 0 ° C x 30 minutes, then at 530 ° C x 30 minutes
Then, a substrate for evaluation was produced.

Evaluation method: (1) Storage stability The viscosity stability of the above paste composition after 24 hours was evaluated. : Stable ×: tendency of thickening was observed

(2) Line Persistence The line persistence was evaluated for the coating film after development, which was carried out when producing the evaluation substrate. : Good ×: dissolved

(3) Space Developability The developed coating film, which was used in producing the evaluation substrate, was evaluated for space developability. : Good ×: Residual development was observed

(4) Presence or Absence of Undercut The undercoat was evaluated for the coating film after the development, which was carried out in producing the evaluation substrate. : No undercut ×: undercut of 5 μm or more was observed

(5) Line shape after firing The film after firing, which was carried out when producing the evaluation substrate, was evaluated for the presence or absence of cracks. ○: No warp ×: Warpage occurred

Table 1 shows the obtained results.

[Table 1] In the above example, the glass paste and the conductive paste were described, but it was also confirmed that the paste was useful as an etching resist used for manufacturing a printed wiring board, a liquid crystal panel, and a PDP. That is, it was confirmed that the positive photosensitive resin composition of the present invention can be easily peeled and removed even by a weak alkaline aqueous solution by irradiating ultraviolet rays.

[0056]

As described above, according to the positive photosensitive resin composition of the present invention, a resin in which a carboxyl group is incorporated into a main chain connecting portion is used as a film-forming component. It has excellent stability and uses a main chain-cleaving type positive resin and photoacid generator, so it shows excellent sensitivity and carboxylic acid is generated quickly by the action of photoacid generator, so high resolution Shows sex. As a result, in manufacturing a plasma display panel or the like, it becomes possible to form a sintered body pattern with high definition and high yield. Further, the positive photosensitive resin composition of the present invention,
Since a resin that breaks the main chain by irradiation with ultraviolet rays to generate a free carboxyl group is used, the resist film can be peeled and removed even with an aqueous solution composed of a weak alkali such as sodium carbonate. As a result, the positive photosensitive resin composition of the present invention is effective as a resist composition that is easy to peel and remove after etching.

[Brief description of the drawings]

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

[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

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/00 C08K 5/00 C08L 67/00 C08L 67/00 G03F 7/004 505 G03F 7/004 505 H01L 21/027 C08J 5/18 CEZ // C08J 5/18 CEZ H01L 21/30 502R (72) Inventor Futoshi Nakanishi 473 Shimokurata-cho, Totsuka-ku, Yokohama-shi, Kanagawa Prefecture (72) Inventor Masahiro Ishidoya 5 Minamiko, Chigasaki-shi, Kanagawa Prefecture −9−5-502 F-term (reference) 2H025 AA00 AA01 AA02 AA03 AA04 AA11 AA16 AB11 AB15 AB17 AC01 AD03 BE00 BE10 BJ10 CB20 CB41 CB55 CC12 CC20 FA17 FA29 4F071 AA69 AB06 AB18 AB28 AC12 AD02 AE09 BA01 002 DA067 DE097 DE107 DE117 DE147 DE157 DL007 EL086 EQ016 EU046 EU186 EV216 EV246 EV296 EV306 EZ006 FD017 FD206 GP03 4J029 AB01 A C01 CA01 CA02 CA03 CA04 CA05 CA06 CB04A CB05A CD03 CD07 KE17

Claims (5)

[Claims] (A) a weight average molecular weight of 1,000 having two or more linking groups represented by the following general formula (1) in the main chain:
A positive-type photosensitive resin composition comprising: (B) a compound capable of generating an acid upon irradiation with active energy rays; Embedded image (A) a weight average molecular weight of 1,000 having two or more linking groups represented by the following general formula (1) in the main chain:
A positive-type photosensitive resin composition comprising: (B) a compound which generates an acid upon irradiation with active energy rays; and (C) an inorganic powder. Embedded image 3. The inorganic powder (C) is at least one selected from (C-1) glass powder, (C-2) ceramic powder, (C-3) black pigment and (C-4) conductive powder.
The positive photosensitive resin composition according to claim 2, wherein the composition contains a seed. 4. The polymer (A) is a polymer of dicarboxylic acid and divinyl ether and has a weight average molecular weight of about 1,0.
The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the composition is a polyhemiacetal ester of 100 to 100,000. 5. The positive photosensitive resin composition according to claim 1, which is in the form of a film or a paste.