JPH11246637A - Photosensitive composition and baked material pattern obtained by using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both an alkali development type photosensitive composition capable of readily forming a baked material pattern such as a high precision electroconductive pattern, a glassy dielectric substance pattern, a fluorescent substance pattern, etc., by a photolithography technique without problems of pattern twist and thinned lines after baking and the baked material pattern obtained from the composition. SOLUTION: This composition comprises (A) a carboxyl group-containing photosensitives polymer obtained by reacting a copolymer of (a) a compound containing a glycidyl group and an unsaturated double bond with (b) a compound containing an unsaturated double bond with (c) a compound containing an unsaturated double band and a carboxyl group and reacting the formed secodary hydroxyl group with (d) a polybasic acid anhydride, (B)a diluent, (C) a photopolymerization initiator, (D) inorganic powder and (E) a stabilizer. The photosensitive composition is applied to a substrate, exposed to the light according to a fixed pattern, developed with an alkali aqueous solution and baked to give a baked material pattern of high precision.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is particularly advantageously applied to the formation of conductive circuit patterns and partition patterns formed on a front substrate and a rear substrate of a plasma display panel, as well as a dielectric pattern, a phosphor pattern, and a black matrix. Conductors for fluorescent display tubes and electronic components,
The present invention relates to a photosensitive composition that can be developed with an aqueous alkaline solution that can also be used to form a resistor and a dielectric, and a fired pattern such as a conductor pattern, a vitreous dielectric pattern, and a phosphor pattern obtained using the composition.

[0002]

2. Description of the Related Art Conventionally, a conductive pattern or a dielectric paste containing an extremely large amount of metal powder or glass powder is generally used for forming a conductor pattern or a dielectric pattern in a plasma display panel, a fluorescent display tube, an electronic component or the like. Thus, the pattern was formed by a screen printing method. However, in recent years, high definition of patterns has been demanded for electronic components and the like. The pattern formation by the conventional screen printing method requires skill, and there are problems such as rubbing and bleeding at the time of printing, alignment and accuracy caused by expansion and contraction of the screen, and it is difficult to cope with a high-definition pattern. ing.

On the other hand, a photosensitive paste containing a copolymer based polymer which is easily depolymerized by heat together with an inorganic powder has been used for high definition.
In many cases, photoreactive groups are not added to the base resin, and the photocuring depth at the time of exposure is insufficient, resulting in poor resolution after development. Also has the disadvantage of lacking. In order to improve the photocuring depth and form a high-definition pattern, it is necessary to add a large amount of a reactive diluent (photocurable monomer). The proportion that remains unreacted increases, and the unreacted material of the reactive diluent gels during firing to generate a firing residue, or causes problems such as pattern distortion or line width shrinkage due to shrinkage due to gelation, In severe cases, disconnection may occur.

On the other hand, photosensitive conductive paste for forming a conductive pattern on a ceramic circuit board includes:
Conductive powder, acrylic copolymer having a carboxyl group and an ethylenically unsaturated group in the side chain, such as methacrylic acid, methyl methacrylate and styrene copolymer with glycidyl acrylate, photoreactivity A paste composition containing a compound and a photopolymerization initiator is disclosed in, for example, JP-A-5-67405 and JP-A-5-271.
No. 576. Such a photosensitive conductive paste can be applied to a substrate and then formed into a conductive circuit pattern by exposure and development. However, it is taught to be baked at 600 to 1,000 ° C. At a firing temperature of 600 ° C. or lower (soda glass is generally used for a substrate of a plasma display panel, firing must be performed at a temperature of 600 ° C. or lower), a firing residue is generated, and an electrode to be formed is formed. It is not suitable for a plasma display panel because it has an effect such as deterioration of circuit conductivity. If an attempt is made to simultaneously incorporate a low melting glass frit into such a composition in order to enable firing at a relatively low temperature,
Poor storage stability of the resulting composition due to strong acidity caused by methacrylic acid in the copolymer resin component, poor coating workability due to gelation and decrease in fluidity, and instability in developability with alkaline aqueous solution The problem arises.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and its basic object is to provide excellent photocurability and to use an extremely large amount of inorganic fine powder. Even when contained, it shows excellent photocuring depth and excellent storage stability, and shows stable adhesion to the substrate in each of the drying, exposure, development, and baking steps. Another object of the present invention is to provide an excellent photosensitive composition. A more specific object of the present invention is
By photolithography technology, high-definition conductive circuit patterns, vitreous dielectric patterns, and phosphor patterns can be formed with good workability and productivity, and the baking process at 600 ° C. or less can be performed without generating a baking residue that adversely affects images. An object of the present invention is to provide a photosensitive composition that can be developed with an aqueous alkali solution. Another object of the present invention is to
An object of the present invention is to provide a high-definition fired product pattern manufactured from such a photosensitive composition by a series of selective exposure, development, and firing steps with high productivity, and a manufacturing technique therefor.

[0006]

According to a first aspect of the present invention, there is provided a compound (a) having a glycidyl group and an unsaturated double bond, and an unsaturated double bond. The copolymer of the compound (b) having a bond is reacted with the compound (c) having an unsaturated double bond and a carboxyl group, and the generated secondary hydroxyl group is reacted with the polybasic anhydride (d). Carboxyl group-containing photosensitive polymer obtained, (B)
A photosensitive composition comprising a diluent, (C) a photopolymerization initiator, (D) an inorganic powder, and (E) a stabilizer is provided.

The photosensitive 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. In the case of a paste-like form, a photosensitive conductive paste composition is obtained when metal fine particles are mainly used as the inorganic powder (D), and a photosensitive glass paste composition is obtained when only glass powder is used. In the case of the paste composition for a black matrix, the paste composition further contains a black pigment. As the inorganic powder, 10
Powders having a particle size of less than a micron can be suitably used. As the metal fine particles in the case of the photosensitive conductive paste, gold, silver,
Copper, palladium, platinum, aluminum, nickel and the like can be used. On the other hand, in the case of photosensitive glass paste,
A low melting point glass having a softening point of 300 to 600 ° C can be suitably used. As black pigments, Fe, Co, Cu, Cr,
A black pigment composed of a metal oxide containing one or more of Mn and Al as a main component can be suitably used.

[0008] According to still another aspect of the present invention, there is provided a fired product pattern formed from the above-described photosensitive composition. For example, when the photosensitive composition is in the form of a paste, the photosensitive composition in the form of a paste is coated on a substrate and dried to form a film. After baking after patterning by selective exposure and development, a baking product pattern with high definition can be obtained. The fired product pattern thus formed becomes a conductor pattern when metal fine particles are used as the inorganic powder (D), and becomes a vitreous dielectric pattern when glass powder is used. In addition, a phosphor pattern can be formed by using a phosphor powder as the inorganic powder.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As described above, when a fired product pattern is formed using a conventional photosensitive paste composition,
Insufficient photocuring depth at the time of exposure causes poor resolution after development, and also causes problems such as pattern distortion and line width shrinkage during baking. The present inventors have conducted intensive studies on such a phenomenon, and as a result, the photosensitive paste composition used for forming the conductor pattern and the dielectric pattern has a very large amount of inorganic powder such as metal fine particles having a very small particle diameter. It has been found that the major factor is that light exposure during exposure is poor due to the presence of, and insufficient photocuring and uneven photocuring are also likely to occur. Such a phenomenon becomes more conspicuous as the film thickness increases and as the film depth increases. Further, as described above, when a monomer component having a high acidity such as methacrylic acid is used as the copolymer resin component, the storage stability of the composition is deteriorated due to the coexistence of metal powder and glass powder.

Therefore, in the photosensitive composition of the present invention, a copolymer resin containing methacrylic acid or the like having a high acidity as a monomer component constituting the main chain is not used as a binder for the inorganic powder, and the side chain is not used. A compound having an unsaturated double bond and a carboxyl group is added as a pendant to a backbone polymer having a glycidyl group, and a carboxyl group is introduced by reacting a polybasic anhydride having a relatively weak acidity with the compound. The first feature is that a photosensitive resin is used. That is, the carboxyl group-containing photosensitive polymer (A) used in the present invention is an epoxy group of a copolymer of a compound (a) having a glycidyl group and an unsaturated double bond and a compound (b) having an unsaturated double bond. To
The unsaturated double bond is reacted with the carboxyl group of the compound (c) having a carboxyl group at such a ratio as to improve the photocurability to the extent that a sufficient photocuring depth can be obtained. It is characterized in that a heavy bond is introduced into a side chain, and a polybasic anhydride (d) is subjected to an esterification reaction with a secondary hydroxyl group generated in the above addition reaction, thereby introducing a carboxyl group into the side chain. Such a carboxyl group-containing photosensitive polymer (A) is excellent in photocurability and baking properties, and does not impair the effect of a stabilizer described later, and contributes to improvement in storage stability of the composition. Further, since it has a carboxyl group in the side chain, it is soluble in an aqueous alkali solution. Therefore, a film formed from the photosensitive composition of the present invention can be stably developed with an aqueous alkali solution after selective exposure.

In the photosensitive composition of the present invention, a low melting point glass powder is used as the inorganic powder (D) when a glass paste is formed. It is preferable to mix a small amount of low melting glass powder even when using other inorganic powder,
Thereby, firing at a temperature of 600 ° C. or less is possible, and the adhesion of the fired product pattern to the substrate is improved.
However, a composition containing such a metal powder or a glass powder has a problem that storage stability is likely to be reduced, and that coating operability is likely to be deteriorated due to gelation or fluidity. Therefore, in the photosensitive composition of the present invention, a stabilizer (E) is used together with the carboxyl group-containing photosensitive polymer (A), diluent (B), photopolymerization initiator (C), and inorganic powder (D). The compounding is the second feature. As a result, the photosensitive composition of the present invention has no problems such as poor storage stability and poor coating workability due to gelation or reduced fluidity, and can easily be formed on a large-area substrate easily by photolithography. Can be formed, and can be sufficiently used even in the firing step at a temperature of 600 ° C. or lower, and a large improvement in yield can be realized.

Hereinafter, each component of the photosensitive composition of the present invention will be described in detail. The carboxyl group-containing photosensitive polymer (A) used in the present invention is an epoxy copolymer of a compound (a) having a glycidyl group and an unsaturated double bond and a compound (b) having an unsaturated double bond in the molecule. The resin is obtained by reacting a carboxyl group of a compound (c) having an unsaturated double bond and a carboxyl group with a group, and reacting a polybasic anhydride (d) with a generated secondary hydroxyl group. Such a carboxyl group-containing photosensitive polymer (A) is preferably blended at a ratio of 5 to 50% by weight based on the total amount of the composition. When the amount of the photosensitive polymer is too small, the distribution of the photosensitive polymer in the film to be formed tends to be uneven, and it is difficult to obtain sufficient photocurability and photocuring depth. Patterning by 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 or the line width is shrunk during firing, which is not preferable.

The carboxyl group-containing photosensitive polymer (A) has a weight average molecular weight of 1,000 to 50,000.
Those having an acid value of 00 and an acid value of 30 to 150 mgKOH / g, preferably 40 to 120 mgKOH / g can be suitably used. When the molecular weight of the carboxyl group-containing photosensitive polymer (A) is lower than 1,000, the adhesion of the film at the time of development is adversely affected. On the other hand, when the molecular weight is higher than 50,000, poor development tends to occur, which is not preferable. .
When the acid value is lower than 30 mgKOH / g, the solubility in an aqueous alkali solution is insufficient, and poor development tends to occur. On the other hand, when the acid value is higher than 150 mgKOH / g, the adhesion of the film deteriorates during development and the photocured portion ( It is not preferable because dissolution of the exposed portion is easily caused.

Specific examples of the compound (a) containing a glycidyl group and an unsaturated double bond in the molecule include glycidyl (meth) acrylate, α-methylglycidyl (meth)
Examples include acrylate and compounds represented by the following formulas (1) to (4), and these can be used alone or in combination of two or more. In this specification, (meth) acrylate is a general term for acrylate and methacrylate.

Embedded image

Compound (b) having an unsaturated double bond
Specific examples of styrene, chlorostyrene, α-methylstyrene; methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, amyl, 2-ethylhexyl, octyl, capryl, nonyl, dodecyl , Hexadecyl, octadecyl,
(Meth) acrylates having cyclohexyl, isobornyl, methoxyethyl, butoxyethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-chloro-2-hydroxypropyl and the like; polyethylene glycol mono (meth) acrylate or polypropylene glycol mono ( (Meth) acrylate; vinyl acetate, vinyl butyrate, vinyl benzoate; acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-
Butoxymethylacrylamide, acrylonitrile, isobutylene and the like can be mentioned, and these can be used alone or in combination of two or more. Among these compounds, styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene are preferably used.

Specific examples of the compound having an unsaturated double bond and a carboxyl group, ie, unsaturated carboxylic acid (c), include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and cinnamic acid. Acid, α-cyanocinnamic acid, β-styrylacrylic acid, β-furfurylacrylic acid and the like can be mentioned, and these can be used alone or in combination of two or more.

Specific examples of the polybasic acid anhydride (d) include:
Succinic anhydride, maleic anhydride, adipic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, itaconic anhydride, methylendmethylenetetrahydrophthalic anhydride, trimellitic anhydride, Examples include pyromellitic dianhydride and the like, and these can be used alone or in combination of two or more.

The compound (a) having the glycidyl group and the unsaturated double bond and the compound (b) having the unsaturated double bond
Copolymerization reaction with, for example, azobisisobutyronitrile, easily proceeds in the presence of a radical polymerization catalyst such as an organic peroxide, and according to a conventional method, for example, a solution polymerization method at about 40 to 130 ° C. And a random copolymer is produced. Further, an addition reaction of the unsaturated carboxylic acid (c) to an epoxy group on a side chain of the obtained copolymer, and a saturated or unsaturated polybasic anhydride to a secondary hydroxyl group generated by the addition reaction. The esterification reaction of the product (d) is carried out by a catalyst such as triethylamine, benzyldimethylamine, methyltriethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine. , Chromium octoate, zirconium octoate or the like is preferably used, and the amount of the catalyst used is preferably 0.1 to 10% by weight based on the reaction raw material mixture. Further, in order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor, for example, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, and the like, and the amount used is preferably based on the reaction raw material mixture. It is 0.01 to 1% by weight. The reaction temperature of the above addition reaction and esterification reaction is preferably 6
0-100 ° C. The reaction ratio of the polybasic acid anhydride (d) is such that the acid value of the carboxyl group-containing photosensitive polymer (A) obtained as described above is 30 to 150 mg KOH.
/ G is preferably adjusted.

The carboxyl group-containing photosensitive polymer (A) has an unsaturated group having a weight average molecular weight of 400 to 4,000.
It is desirable to adjust the content to be one per 0, more preferably one per 500 to 2,000 weight average molecular weight. When the amount of the unsaturated group to be introduced is larger than the above ratio, phenomena such as halation occur at the time of image formation by selective exposure, and it becomes difficult to form a sharp pattern. Is more likely to occur. Furthermore, when there are many unsaturated groups, curing shrinkage at the time of radical polymerization at the time of exposure, or a coating film becomes too hard after radical polymerization, becomes brittle, and easily causes poor adhesion to a substrate. On the other hand, when the amount of unsaturated groups is too small, the exposure amount at the time of pattern formation is required to be higher, or the pattern is applied in the process of development and washing, and it is difficult to form a sharp pattern. Easy to be.

As the diluent (B) to be added to the photosensitive composition of the present invention, an organic solvent and / or a reactive diluent containing an unsaturated group can be used. Representative examples of the organic solvent include toluene, xylene, and tetramethylbenzene, and Solvesso # 100, Solvesso # 150, Solvesso # 200, and Exxon Aromatic Naphtha No. 2. Laws, H made by Shell Co., Ltd.
AWS, VLAWS, Shellsol D40, D70, D
100, 70, 71, 72, A, AB, R, DOSB,
Aromatic solvents such as DOSB-8; Exxon Naphtha No. 5, no. 6, no. 7. Aliphatic solvents such as Exxon orderless solvent and Exxon rubber solvent; methanol, ethanol, propanol, isopropanol, butanol, hexanol,
Alcohol solvents such as cellosolve, butyl cellosolve, carbitol, and butyl carbitol; and ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, carbitol acetate, methyl lactate, ethyl lactate, and butyl lactate. These organic solvents can be used alone or as a mixture of two or more. However, a solvent containing no hydroxyl group is preferable because a composition having better storage stability can be obtained.

Representative examples of the reactive diluent containing an unsaturated group include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; ethylene glycol; Mono- or di (meth) acrylates of glycols such as methoxytetraethylene glycol and polyethylene glycol; (meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; N, N-dimethyl Aminoalkyl (meth) such as aminoethyl (meth) acrylate
Acrylates; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and trishydroxyethyl isocyanurate; and polyhydric (meth) acrylates of ethylene oxide or propylene oxide adduct thereof; Phenoxyethyl (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, and other phenolic ethylene oxide or propylene oxide adducts (meth) acrylates; glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate (Meth) acrylates of glycidyl ether such as melamine (meth) acrylate; Can. Further, a reaction product of a hydroxyl group-containing (meth) acrylate and an anhydride of a polyvalent carboxylic acid compound may be used. These unsaturated group-containing reactive diluents can be used alone or in combination of two or more, and not only act as a diluent, but also for promoting photocurability of the composition and improving developability. Also contributes.

The organic solvent and the reactive diluent having an unsaturated group are used alone or as a mixture of two or more. The compounding ratio of these diluents (B) can be mixed in an appropriate amount according to the method of applying the composition, but is generally 1 to 200 per 100 parts by weight of the carboxyl group-containing photosensitive polymer (A). Suitably, parts by weight, preferably 20 to 100 parts by weight, are suitable.

Specific examples of the photopolymerization initiator (C) 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, 2-benzyl Aminoacetophenones such as -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1;
Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropyl Thioxanthones such as thioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal;
Examples thereof include benzophenones such as benzophenone; xanthones; these known and commonly used photopolymerization initiators can be used alone or in combination of two or more. The mixing ratio of these photopolymerization initiators (C) is 1 to 100 parts by weight of the carboxyl group-containing photosensitive polymer (A).
-20 parts by weight are preferred.

Further, the above-mentioned photopolymerization initiator (C)
Is N, N-dimethylaminobenzoic acid ethyl ester,
N, N-dimethylaminobenzoic acid isoamyl ester,
It can be used in combination with one or more photosensitizers such as tertiary amines such as pentyl-4-dimethylaminobenzoate, triethylamine and triethanolamine. Furthermore, when a deeper photo-curing depth is required, CG manufactured by Ciba Specialty Chemicals, which initiates radical polymerization in the visible region, if necessary.
A titanocene-based photopolymerization initiator such as I784, a leuco dye, or the like can be used in combination as a curing aid.

Specific examples of the inorganic powder (D) used when formulating the photosensitive composition of the present invention as a conductive paste include metal fine particles (D-1) or metal fine particles and glass fine particles (D-2). And mixtures thereof. Metal fine particles (D
As -1), gold, silver, copper, palladium, platinum, aluminum, nickel and the like and alloys thereof can be used.
The above metal powders can be used alone or in combination of two or more kinds.
Submicron particle sizes are preferred. These metal powders can be used alone or in combination of two or more in the form of sphere, block, flake, or dendrite.

The amount of the metal powder is from 25 to 1,0 per 100 parts by weight of the carboxyl group-containing photosensitive polymer (A).
A ratio of 00 parts by weight is appropriate. If the compounding amount of the metal powder is less than 25 parts by weight, line width shrinkage or disconnection of the conductor circuit is liable to occur. On the other hand, if the compounding amount exceeds 1,000 parts by weight, light transmission is impaired, It becomes difficult to obtain sufficient photocurability. Further, in order to improve the strength of the film after firing and the adhesion to the substrate, a glass powder (D
-2) can be added in the range of 1 to 30 parts by weight based on 100 parts by weight of the metal powder.

As the glass powder (D-2) used when formulating the photosensitive composition of the present invention as a glass paste, a low-melting glass having a softening point of 300 to 600 ° C. is used, and lead oxide, bismuth oxide, Alternatively, those having an average particle diameter of 10 μm or less containing zinc oxide as a main component can be suitably used. When the total amount of the carboxyl group-containing photosensitive polymer (A), the diluent (B) and the photopolymerization initiator (C) is 100 parts by weight, the compounding amount of the glass powder is 50 to 2,
An appropriate ratio is 000 parts by weight.

Preferable examples of the glass powder containing lead oxide as a main component are as follows.
82%, B ₂ 0 ₃ is 0.5 to 22%, SiO ₂ is 3-3
2% Al ₂ O ₃ is 0 to 12% BaO 0-10%
ZnO is 0 to 15%, TiO ₂ is 0 to 2.5%, Bi ₂
O ₃ has a composition of 0 to 25% and a softening point of 420 to 59
A non-crystalline frit at 0 ° C.

Preferred examples of the glass powder containing bismuth oxide as a main component include Bi ₂ O in terms of% by weight on an oxide basis.
₃ is 35~88%, B ₂ 0 ₃ is 5 to 30% SiO ₂ is 0 to 20% Al ₂ O ₃ 0 to 5 percent, BaO 1 to 25
%, ZnO having a composition of 1 to 20%, and a softening point of 420
Non-crystalline frit having a temperature of ５590 ° 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.
~60%, K ₂ O is 2~15%, B ₂ 0 ₃ is 25 to 45
%, SiO ₂ is 1~7%, Al ₂ O ₃ is 0%, B
aO has a composition of 0 to 20%, MgO has a composition of 0 to 10%,
A non-crystalline frit having a softening point of 420 to 590 ° C is exemplified.

When the color tone of the paste is black, Fe, C
A black pigment made of a metal oxide containing one or more of o, Cu, Cr, Mn, and Al as a main component can be added.

As the inorganic powder (D-3) used when formulating the photosensitive composition of the present invention into a phosphor paste, various phosphor powders can be used depending on the application. Strontium oxide, barium oxide, alumina, cerium oxide, etc. in the short period rate table II
At least one of the metal oxides of the elements belonging to Group a, IIIa, and IIIb contains S as an activator or co-activator.
c, Y, La, Ce, Pr, Nd, Sm, Eu, Gd,
A long afterglow fluorescent substance having a ceramic structure obtained by mixing and sintering at least one rare earth element selected from Tb, Dy, Ho, Er, Tm, Yb and Lu;
A fluorescent substance such as zinc or alkaline earth sulfide, which is a typical phosphor, can be used. Generally, (Y, Gd) BO ₃ : E is used for the fluorescent layer of the plasma display panel.
u (yttrium and gadolinium borate with europium as the emission center, red emission), Zn ₂ SiO ₄ :
Mn (zinc silicate form a light emitting center manganese, green light _{emission), BaO · 6Al 2 O 3} : Mn ( green emission), Ba
MgAl ₁₄ O ₂₃ : Eu (barium magnesium aluminate with europium emission center, blue emission), B
aMgAl ₁₀ O ₁₇ : Eu (blue light emission) or the like is used. The average particle size of these phosphor powders is desirably 10 μm or less, preferably 5 μm or less, and the compounding ratio is the same as in the case of the metal powder.

Since the inorganic powder used in the present invention preferably has a particle size of 10 μm or less, the properties of the inorganic powder are impaired for the purpose of preventing secondary aggregation and improving dispersibility. Use an organic acid, an inorganic acid, a silane coupling agent, a titanate-based coupling agent, an aluminum-based coupling agent, or the like that has been surface-treated in advance, or the above-described treating agent when the photosensitive composition is formed into a paste. Is preferably added. As a method of treating the inorganic powder, after dissolving the surface treating agent as described above in an organic solvent or water,
After adding and stirring the inorganic powder and distilling off the solvent, about 50 to 2
It is desirable to perform a heat treatment at 00 ° C. for 2 hours or more.

In the photosensitive composition according to the present invention, a compound having an effect of complexing with a metal or oxide powder or forming a salt is added as a stabilizer (E) in order to improve the storage stability of the composition. I do. As the stabilizer (E), inorganic acids, organic acids, phosphoric acid compounds (inorganic phosphoric acid, organic phosphoric acid)
Such acids can be suitably used. Such a stabilizer is preferably added in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the inorganic powder (D).

Examples of the inorganic acid include nitric acid, sulfuric acid, hydrochloric acid, boric acid and the like. The organic acids include formic acid, acetic acid, acetoacetic acid, citric acid, isocitric acid, anisic acid,
Propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid,
Azelaic acid, tillic acid, parelic acid, caproic acid, isocaproic acid, enanthic acid, caprylic acid, pelargonic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, behenic acid , Oxalic acid, malonic acid, ethyl malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, pyruvic acid, piperonylic 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, isopropylbenzoic acid, salicylic acid, isocaproic acid, crotonic acid, isocrotonic acid, acrylic acid, methacrylic acid, tiglic acid,
Ethyl acrylic acid, ethylidene propionic acid, dimethyl acrylic acid, citronellic acid, undecenoic acid, undecanoic acid, oleic acid, elaidic acid, erucic acid, brassic acid, phenylacetic 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, pelargonic acid, benzylic acid, enanthic acid, elaidic acid, erucic acid, oxalosuccinic acid, oxaloacetic acid, octanoic acid, caprylic acid, gallic acid, mandelic acid Myristic acid, mesaconic acid, methylmalonic acid, mellitic 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. 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, n-butyl phosphate, methyl phosphite, ethyl phosphite, propyl phosphite, butyl phosphite, phenyl phosphite, dimethyl phosphite, phosphorous acid Diethyl, dibutyl phosphite, dipropyl phosphite, diphenyl phosphite, isopropyl phosphite, diisopropyl phosphite,
N-butyl-2-ethylhexylhydroxyethylenediphosphonate, 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 phosphate, (2-hydroxyethyl) methacrylate Rate acid phosphate, and the like.

Other acids include 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 composition of the present invention may contain various pigments, especially heat-resistant inorganic pigments, silicone-based and acrylic-based defoaming / leveling agents, as long as the desired properties are not impaired. And other additives. Furthermore, if necessary, a known and commonly used antioxidant for preventing oxidation of the conductive metal powder, a thermal polymerization inhibitor for improving thermal stability during storage, and a substrate for firing. Fine particles such as metal oxides, silicon oxides, and boron oxides as binding components can also be added.

As described above, the photosensitive resin set of the present invention can be used as a conductive paste, a glass paste, a phosphor paste, etc., and these can be used in the form of a film. It is applied to various substrates such as a glass plate and a ceramic plate by an appropriate method such as a screen printing method, a curtain coating method, a roll coating method, a bar coating method, and a blade coating method. After the coating, a hot air circulation drying oven, far infrared drying oven, etc.
It is dried at 0 to 120 ° C. for about 5 to 40 minutes to obtain a tack-free coating film. Thereafter, a predetermined conductor pattern, a vitreous dielectric pattern, and a phosphor pattern are formed by performing selective exposure, development, and baking.

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, or the like is used. Exposure amount is 50-100
0 mJ / cm ² is preferred.

As the developing step, a spray method, an immersion method or the like is used. As the developing solution, an aqueous solution of a metal alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium silicate, or an aqueous solution of an amine such as monoethanolamine, diethanolamine or triethanolamine, 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 photosensitive polymer in the composition is saponified and the uncured portion (unexposed portion) is removed. It is not limited to the developer. Further, it is preferable to perform washing with water or acid neutralization to remove an unnecessary developer after the development.

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

[0043]

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.

Synthesis Example 1 A three-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser was charged with 200 parts of methyl methacrylate.
g, 142 g of glycidyl methacrylate and 300 g of diethylene glycol monoethyl ether acetate
Azobisisobutyronitrile was added as a catalyst, and the mixture was reacted at 80 ° C. for 10 hours with stirring. Thereafter, 88 g of methacrylic acid, 0.5 g of triphenylphosphine and 0.2 g of hydroquinone as a polymerization inhibitor were measured and dropped into the above reaction solution with a dropping funnel.
For 8 hours, and then tetrahydrophthalic anhydride 1
40 g was added and reacted at 80 ° C. for 5 hours to obtain a carboxyl group-containing photosensitive polymer (A-1). The acid value of the resin obtained at this time was 90 mgKOH / g.

Synthesis Example 2 In a three-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, 28 t-butyl methacrylate was added.
4 g, 142 g of glycidyl methacrylate, 300 g of diethylene glycol monoethyl ether acetate
g, azobisisobutyronitrile was added as a catalyst and reacted at 80 ° C. for 10 hours with stirring. Thereafter, 88 g of methacrylic acid, 0.5 g of triphenylphosphine and 0.2 g of hydroquinone as a polymerization inhibitor were measured and dropped into the above reaction solution with a dropping funnel.
For 8 hours, further added 90 g of succinic anhydride, and reacted at 80 ° C. for 5 hours to obtain a carboxyl group-containing photosensitive polymer (A-2). The acid value of the resin obtained at this time was 95 mgKOH / g.

Comparative Synthesis Example 1 In a three-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, 200 methyl methacrylate was added.
g, 172 g of methacrylic acid and 300 g of diethylene glycol monoethyl ether acetate, azobisisobutyronitrile was added as a catalyst, and the mixture was reacted at 80 ° C. for 10 hours with stirring. Thereafter, 142 g of glycidyl methacrylate and 0.1 g of triphenylphosphine were added.
5 g and 0.2 g of hydroquinone as a polymerization inhibitor were weighed and dropped into the above reaction solution with a dropping funnel.
The reaction was carried out for an hour to obtain a carboxyl group-containing photosensitive polymer (A '). The acid value of the resin obtained at this time is 110
mg KOH / g.

Examples 1 to 4 and Comparative Examples 1 and 2 The respective resins obtained in the above Synthesis Examples were blended together with other components at the composition ratios shown in Table 1 below. Paste by milling with a roll mill,
A photosensitive composition was prepared.

Examples 5 to 8 and Comparative Examples 3 and 4 Using the respective resins obtained in the above Synthesis Examples, the compositions shown in Table 2 below together with other similar components except that the kind and the amount of the stabilizer were changed. After mixing with a stirrer, the mixture was kneaded with a three-roll mill to form a paste to prepare a photosensitive composition.

Characteristic test: The photosensitive composition pasted as described above was applied on a glass substrate to a thickness of 40 μm using a 200-mesh stainless steel screen.
After drying in a hot air drying oven at 80 ° C for 20 minutes, the line /
Space pattern is L / S = 30/150 (micron)
680 GW made by Oak Co., Ltd.
After irradiating with ultraviolet light by an exposure machine, 30% of 1% Na ₂ CO
₃ Developed with an aqueous solution at a water pressure of 1.5 kgf / cm ² for 1 minute, washed with water and dried. Then, at 450 ° C. in a firing furnace, 3
Baking for 0 minutes, and further raising the temperature to 550 ° C.
The substrate was baked for 0 minutes to prepare an evaluation substrate, and the following items were evaluated.

Storage stability: The storage stability was determined by storing the prepared paste at 20 ° C. for 6 days, 1 month, 2 months or 3 days.
Evaluation was made based on the rate of thickening after a lapse of months. ：: Thickening rate less than 15% Δ: Thickening rate 15% to 30% ×: Thickening rate 30% or more

Resolution: UV irradiation was performed with a line width of 30 μm.
Use a negative film of space 150μm, 200m
The test was performed at J / cm ² . The resolution was evaluated by observing the line width reproducibility, shape, disconnection, and the like with an optical microscope, and based on the following criteria. ：: good in all. Δ: Difference in line width reproducibility of ± 10 μm or more was found, and the shape was irregular, but there was no disconnection. C: Difference in line width reproducibility of ± 15 μm or more was found, the shape was irregular, and disconnection was observed.

Baking line shape: 5 ° C.
/ Min at 400 ° C / min.
After holding for minutes, firing the organic component, the temperature was raised again at 5 ° C./minute, and firing at 550 ° C. for 30 minutes was observed with an optical microscope. Good: The shape before firing is maintained. Poor: The shape before firing was not maintained, and the line was broken or distorted.

Specific resistance: The specific resistance is 0.4 cm × 10 c
The resistance value and the film thickness were measured and calculated in the pattern of m. The evaluation results of the various properties are shown in Tables 1 and 2 below.

[Table 1]

[0054]

[Table 2]

[0055]

As described above, the alkali-developable photosensitive composition of the present invention is excellent in storage stability, excellent in photocurability, adhesion to a substrate and baking properties, and is excellent in photocuring during exposure. Since the depth is large, it is possible to stably form a high-definition fired product pattern having no problems such as pattern distortion after firing and line width shrinkage. In addition, because of its excellent photocurability and resolution, it is possible to form a high-definition pattern even with a relatively thick film, and the minimum exposure amount that can form the same line / space pattern with the same film thickness is small. This is advantageous from the viewpoint of energy saving. Further, it is possible to easily form a high-definition conductor pattern, a vitreous derivative pattern, a phosphor pattern, and other fired product patterns on a large-area substrate by photolithography with good workability.
The firing step at a temperature of 00 ° C. or less can be sufficiently employed, and a significant improvement in yield can be realized.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 201/08 C09D 201/08 H01B 3/30 H01B 3/30 Z H01J 9/02 H01J 9/02 F 9/20 9/20 // C08F 8/14 C08F 8/14

Claims (7)

[Claims] 1. A copolymer of (A) a compound (a) having a glycidyl group and an unsaturated double bond and a compound (b) having an unsaturated double bond has an unsaturated double bond and a carboxyl group. Reacting the compound (c), and reacting a polybasic anhydride (d) with the generated secondary hydroxyl group, a carboxyl group-containing photosensitive polymer, (B) a diluent, (C) a photopolymerization initiator, A photosensitive composition comprising (D) an inorganic powder and (E) a stabilizer. 2. The photosensitive composition according to claim 1, comprising 5 to 50% by weight of the carboxyl group-containing photosensitive polymer (A). 3. The carboxyl group-containing photosensitive polymer (A) has a weight average molecular weight of 1,000 to 50,000.
And an unsaturated group having a weight average molecular weight of 400 to 4,000.
The photosensitive composition according to claim 1, wherein the photosensitive composition is contained at a ratio of one per unit. 4. The photosensitive composition according to claim 1, wherein the inorganic powder (D) is metal fine particles and / or glass powder and / or a black pigment. . 5. The method according to claim 1, wherein the stabilizer (E) is an inorganic acid, an organic acid,
5. The composition according to claim 1, wherein the at least one acid is selected from the group consisting of inorganic phosphoric acid and organic phosphoric acid.
The photosensitive composition according to any one of the above. 6. The photosensitive composition according to claim 1, which is formed into a film. 7. A fired product pattern obtained by patterning a film of the photosensitive composition according to any one of claims 1 to 6 adhered on a substrate and firing the film.