JP2008146042A - Paste composition, forming method of pattern using same, and its pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a paste composition suitable for a laser direct imaging device using a laser oscillation light source having a maximum wavelength of 350-420 nm, useful for efficiently forming a fine pattern, and excellent in storage stability. <P>SOLUTION: The alkali developable paste composition comprises (A) a carboxylic resin, (B) glass frit, (C) inorganic powder, (D) a compound having at least one radically polymerizable unsaturated group within a molecule, (E-1) an oxime ester photopolymerization initiator such as 2-(acetyloxyiminomethyl)thioxanten-9-one, and (F) a sulfur compound such as 2-mercaptobenzothiazole. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a paste composition suitable for forming a black matrix pattern or a conductive pattern useful for a thin display, a pattern forming method using the same, a pattern thereof, and a plasma display panel. More specifically, it is suitable for a laser direct imaging apparatus using a laser oscillation light source having a maximum wavelength of 350 nm to 420 nm, useful for efficiently forming a fine black matrix pattern or a conductive pattern, and for storage stability. Black paste composition that is excellent and can be effectively applied to exposure methods other than laser direct imaging apparatuses, paste compositions such as silver paste compositions, and methods for forming black matrix patterns and conductive patterns using the same, The present invention relates to a black matrix pattern, a conductive pattern, and a plasma display panel.

  Conventionally, a black matrix pattern is used for a front plate of a thin display. And the formation method is, for example, applying a black matrix pattern resist on a glass substrate and drying to form a coating film, exposing the image through a photomask on which the circuit and electrode patterns are drawn, and then exposing the exposed portion. The resist layer corresponding to the circuit and electrode pattern is formed by developing with an alkaline aqueous solution using the difference in solubility in the developer in the unexposed area and the unexposed area, and a black matrix pattern that adheres to the glass substrate is formed by baking. Was.

  In addition, a conductive pattern is formed as an electrode on a glass substrate or the like of the plasma display. Then, for example, a silver-containing resist is coated and dried on a glass substrate to form a coating film, and the coating film is exposed to an image through a photomask on which an electrode pattern is drawn. The silver pattern which adhered to the glass substrate was formed by forming and baking the resist layer corresponding to an electrode pattern by developing with an alkaline aqueous solution using the difference in solubility with respect to the solution.

  However, in these pattern exposure methods, the photomask is not completely free of defects, and the formed pattern may be damaged, or the photomask and the glass substrate may be displaced due to expansion and contraction. Pattern exposure was difficult, and it was difficult to reduce the defective rate in the production of large panels. Moreover, since time and cost are required for photomask preparation, it has been regarded as a problem that the cost of the photomask increases, particularly in the case of production of a small quantity of various products or trial production.

  For these reasons, a laser direct imaging method (hereinafter referred to as LDI) in which a circuit created by CAD (Computer Aided Design) is directly drawn by laser light has been reviewed. Since LDI draws patterns directly from CAD data, it can efficiently produce a small quantity and a wide variety of products, and since it does not use a photomask, alignment is accurate and scaling correction is easy. There are many advantages such as eliminating the need for foreign matter adhesion, dirt, and scratch management.

However, since LDI directly draws by laser scanning, it has the disadvantage that the tact time is long and the throughput is insufficient as compared with the case where exposure is performed all at once using a photomask. In order to improve the throughput, it is necessary to increase the scanning speed of the laser. However, since the sensitivity of the conventional photosensitive paste composition is insufficient (appropriate exposure = 300 to 500 mJ / cm ² ), scanning is performed. There was a problem that it was difficult to increase the speed.

On the other hand, as a composition to be exposed by laser scanning, a composition containing a specific dye sensitizer and a titanocene compound (see, for example, Patent Document 1 and Patent Document 2) or a specific bisacylphosphine. A laser photosensitive composition containing oxide (for example, see Patent Document 3) has been proposed, but a sufficient photosensitive speed has not been obtained.
JP 2002-351071 A (Claims) JP 2002-351072 A (Claims) JP 2004-45596 A (Claims)

  The present invention has been developed in view of the above problems, and its main purpose is suitable for a laser direct imaging apparatus using an active energy ray such as a laser oscillation light source having a maximum wavelength of 350 nm to 420 nm. It is an object of the present invention to provide a paste composition that is useful for efficiently forming a pattern and has excellent storage stability, a method for forming a pattern using the paste composition, and the pattern.

  Furthermore, this invention is providing the paste composition which can be applied effectively also to exposure methods other than a laser direct imaging apparatus, the formation method of a pattern using the same, and its pattern.

  In order to solve the above problems, the present invention comprises the following arrangement.

(1) (A) carboxyl group-containing resin, (B) glass frit, (C) inorganic powder, (D) a compound having at least one radically polymerizable unsaturated group in one molecule, and (E-1) ) An oxime ester photopolymerization initiator having a functional group represented by the following general formula (I):

(In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
And (F) a sulfur compound represented by the following general formula (II)

(In the formula, R ³ represents an alkyl group, an aryl group or a substituted aryl group, R ⁴ represents a hydrogen atom or an alkyl group, and R ³ and R ⁴ are bonded to each other to form an oxygen, sulfur and nitrogen atom. (A group of nonmetallic atoms necessary to form a 5-membered to 7-membered ring which may contain a selected heteroatom.)
An alkali-developable paste composition comprising:

(2) The oxime ester photopolymerization initiator (E-1) is represented by the following general formula (III):

(In the formula, one or two R ⁵ are represented by the following general formula (I) (provided that when two R ⁵ are represented by the general formula (I), R ⁵ is different from each other)). The remaining R ⁵ represents a hydrogen atom, a methyl group, a phenyl group, or a halogen atom (provided that each R ⁵ is different).

In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

The alkali development type paste composition as described in (1) above.

(3) The carboxyl group-containing resin (A) is further (A-1) a carboxyl group-containing resin having one or more radically polymerizable unsaturated groups (1) or (2) The alkali development type paste composition as described.

(4) Furthermore, (E-2) a phosphine oxide photopolymerization initiator containing a structure represented by the following general formula (IV)

In the formula, R ⁶ and R ⁷ are each independently substituted with a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or a halogen atom, an alkyl group or an alkoxy group. Or any one of them represents a carbonyl group having 1 to 20 carbon atoms.

The alkali development type paste composition according to any one of (1) to (3), characterized by comprising:

(5) In the composition according to (4), the amount of the oxime ester photopolymerization initiator (E-1) represented by the general formula (I) is phosphine represented by the general formula (IV). An alkali development type paste composition characterized by being less than the blending amount of the oxide photopolymerization initiator (E-2).

(6) The alkali developing paste composition according to any one of (1) to (5), further comprising (G) boric acid.

(7) Further, (H) a phosphorus compound represented by the following general formula (V) or general formula (VI)

The alkali development type paste composition according to any one of (1) to (6), wherein the paste composition is an alkali development type paste composition.

(8) The compounding amount of the compound (E-1) represented by the general formula (I) is 0.1 to 1.0% by mass of the total amount of the composition (1) to (7) The alkali development type paste composition according to any one of the above.

(9) The alkali developing paste composition according to any one of (1) to (8), wherein the inorganic powder (C) is a black pigment (C-1).

(10) The alkali developing paste composition according to any one of (1) to (8), wherein the inorganic powder (C) is a silver powder (C-2).

(11) The composition according to any one of (1) to (10), wherein the coating film obtained by coating and drying has an absorbance of 0.1 to 0.8 per 1 μm of film thickness. An alkali developing paste composition.

(12) A pattern forming method using the composition according to any one of (1) to (11),
(1) A pattern drawing process using an active energy ray having a maximum wavelength of 350 nm to 420 nm;
(2) a step of selectively forming a pattern by developing with a dilute alkaline aqueous solution;
(3) a step of firing at 400 to 600 ° C .;
A method of forming a pattern, comprising:

(13) The pattern forming method according to (12), wherein the pattern is a black matrix pattern and / or a conductive pattern.

(14) A pattern obtained by the pattern forming method according to (12) or (13).

(15) A plasma display panel including the pattern according to (14).

  Since the paste composition such as the black paste composition and the silver paste composition of the present invention exhibits excellent photocurability with respect to active energy rays including a laser oscillation light source having a maximum wavelength of 350 nm to 420 nm, the exposure apparatus The laser direct imaging system can be used, and there is no positional displacement due to the expansion and contraction of the photomask and glass substrate that has occurred in the conventional exposure method, and there is no pattern loss due to foreign matter adhering to the photomask. High black matrix patterns and conductive patterns can be formed.

  In addition, the use of a laser direct imaging apparatus eliminates the need for a photomask, facilitates the transfer from design to manufacturing, and further reduces the product cost by reducing the defect rate.

  In particular, by blending the sulfur compound represented by the general formula (II), it is possible to form a highly accurate pattern having sufficient sensitivity to active energy rays including laser light.

  The paste composition of the present invention comprises (A) a carboxyl group-containing resin, (B) a glass frit, (C) an inorganic powder, (D) a compound having at least one radically polymerizable unsaturated group in one molecule, And (E-1) an oxime ester photopolymerization initiator represented by the general formula (I), (F) a laser having a maximum wavelength of 350 nm to 420 nm, containing a sulfur compound represented by the general formula (II). It has a feature that it exhibits excellent photocurability with respect to active energy rays including an oscillation light source.

  Furthermore, in a suitable aspect, the said composition contains (G) boric acid, and can provide the composition excellent in storage stability. Moreover, the composition which contains (H) phosphorus compound and was excellent in storage stability can be provided.

(A) Carboxyl group-containing resin Hereinafter, each component of the paste composition of the present invention will be described in detail.

  As the carboxyl group-containing resin (A) contained in the paste composition of the present invention, a known and commonly used resin compound containing a carboxyl group in the molecule can be used.

  Specific examples include the resins listed below.

(1) a carboxyl group-containing resin obtained by copolymerizing with an unsaturated carboxylic acid such as (meth) acrylic acid and one or more other compounds having an unsaturated double bond;
(2) Glycidyl (meth) acrylate or 3,4-epoxycyclohexyl is a copolymer of an unsaturated carboxylic acid such as (meth) acrylic acid and one or more other compounds having an unsaturated double bond. A carboxyl group-containing photosensitive resin obtained by adding an ethylenically unsaturated group as a pendant by a compound having an epoxy group and an unsaturated double bond, such as methyl (meth) acrylate, or (meth) acrylic acid chloride,
(3) Copolymerization of a compound having an unsaturated double bond with an epoxy group such as glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acrylate, and a compound having an unsaturated double bond other than that A carboxyl group-containing photosensitive resin obtained by reacting an unsaturated carboxylic acid such as (meth) acrylic acid with the coalescence and reacting a polybasic acid anhydride with the generated secondary hydroxyl group,
(4) To a copolymer of an acid anhydride having an unsaturated double bond such as maleic anhydride and a compound having an unsaturated double bond other than that, a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; A carboxyl group-containing photosensitive resin obtained by reacting a compound having an unsaturated double bond,
(5) a carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting the generated hydroxyl group with a saturated or unsaturated polybasic acid anhydride,
(6) After reacting a hydroxyl group-containing polymer such as a polyvinyl alcohol derivative with a saturated or unsaturated polybasic acid anhydride, the resulting carboxylic acid is reacted with an epoxy group and a compound having an unsaturated double bond in one molecule. Hydroxyl and carboxyl group-containing photosensitive resin obtained by
(7) a polyfunctional epoxy compound, an unsaturated monocarboxylic acid, at least one alcoholic hydroxyl group in one molecule, and a compound having one reactive group other than an alcoholic hydroxyl group that reacts with an epoxy group A carboxyl group-containing photosensitive resin obtained by reacting the reaction product with a saturated or unsaturated polybasic acid anhydride,
(8) Saturated or unsaturated polybasic with respect to the primary hydroxyl group in the modified oxetane resin obtained by reacting an unsaturated monocarboxylic acid with a polyfunctional oxetane compound having at least two oxetane rings in one molecule. A carboxyl group-containing photosensitive resin obtained by reacting an acid anhydride, and (9) containing a carboxyl group obtained by reacting an unsaturated monocarboxylic acid with a polyfunctional epoxy resin and then reacting with a polybasic acid anhydride. Examples of the resin further include a carboxyl group-containing photosensitive resin obtained by reacting a compound having one oxirane ring and one or more ethylenically unsaturated groups in the molecule. Not.

  Among these examples, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecules (2) and (3) is preferable from the viewpoint of photocurability and baking properties. .

  In addition, in this specification, (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

  Since the carboxyl group-containing resin (A) as described above has a large number of free carboxyl groups in the side chain of the backbone polymer, development with a dilute aqueous alkali solution is possible.

  Moreover, the acid value of the said carboxyl group-containing resin (A) is the range of 40-200 mgKOH / g, More preferably, it is the range of 45-120 mgKOH / g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds and the line becomes thinner than necessary. Depending on the case, the exposed portion and the unexposed portion are not distinguished from each other by dissolution and peeling with a developer, which makes it difficult to draw a normal resist pattern.

  Moreover, although the weight average molecular weight of the said carboxyl group-containing resin (A) changes with resin frame | skeleton, generally what is in the range of 2,000-150,000, Furthermore, 5,000-100,000 is preferable. When the weight average molecular weight is less than 2,000, the tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, and the film may be reduced during development, and the resolution may be greatly deteriorated. On the other hand, when the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.

  The amount of the carboxyl group-containing resin (A) is preferably 10 to 80% by mass, more preferably 15 to 15% in the total composition when (C-1) black pigment is used as (C). 50% by mass. Moreover, when using (C-2) silver powder as (C), Preferably it is 2-50 mass% in a whole composition, More preferably, it is 4-30 mass%. If the blending amount is too small, the coating film strength decreases, which is not preferable. On the other hand, when the amount is too large, the viscosity becomes high, and the coating property and the like are lowered, which is not preferable.

(B) Glass frit As the glass frit (B) used in the paste composition of the present invention, a low-melting glass frit having a softening point of 300 to 600 ° C. is used, and the main component is lead oxide, bismuth oxide, or zinc oxide. Can be suitably used. From the viewpoint of resolution, it is preferable to use those having an average particle size of 20 μm or less, preferably 5 μm or less. Preferred examples of the glass powder based on lead oxide, in mass percent on the oxide basis, PbO is 48 to _82%, B 2 _{0 3} is 0.5 to 22%, SiO ₂ is from 3 to 32%, Al ₂ O ₃ has a composition of 0-12%, BaO 0-10%, ZnO 0-15%, TiO ₂ 0-2.5%, Bi ₂ O ₃ 0-25%, softening Non-crystalline frit having a point of 420 to 590 ° C can be mentioned.

Preferred examples of the glass powder based on bismuth oxide, in mass percent on the oxide basis, _Bi 2 _{O 3} is 35 to _88%, B 2 _{O 3} is 5 to 30%, SiO ₂ is 0 Examples thereof include an amorphous frit having a composition of 20%, Al ₂ O ₃ of 0 to 5%, BaO of 1 to 25%, ZnO of 1 to 20%, and a softening point of 420 to 590 ° C.

Further, preferred examples of the glass powder based on zinc oxide, at a weight percent on the oxide basis, ZnO is 25 to 60%, _{K 2} O is 2 to _15%, B 2 _{O 3} is 25% to 45% SiO ₂ is 1 to 7%, Al ₂ O ₃ is 0 to 10%, BaO is 0 to 20%, MgO is 0 to 10%, and the softening point is 420 to 590 ° C. Frit.

  The blending amount of such a glass frit is preferably 1 to 20% by mass, more preferably 2 to 10% by mass in the total composition. If the blending amount is too small, the adhesion to the substrate is poor, and if the blending amount is too large, the composition may be thickened or gelled.

(C) Inorganic powder (C-1) Black pigment As the black pigment (C-1) used in the black paste composition of the present invention, a single metal such as Cu, Fe, Cr, Mn, Co, Ru, La, etc. A composite oxide composed of two or more oxides and / or metal elements can be suitably used. The average particle diameter is preferably 10 μm or less, more preferably 2.5 μm or less from the viewpoint of resolution. On the other hand, from the point of blackness, an average particle size of preferably 1.0 μm or less, more preferably 0.6 μm or less is suitable.

Among such black pigments, it is particularly preferable to use cobalt trioxide (Co ₃ O ₄ ) fine particles having a specific surface area of 1.0 to ²⁰ m ² / g. This is because when the specific surface area is less than 1.0 m ² / g, the accuracy of pattern formation by exposure decreases, and it becomes difficult to obtain a fired film having linearity of the line edge or sufficient blackness. On the other hand, if it exceeds 20 m ² / g, the surface area of the particles becomes too large and an undercut tends to occur during development.

  Moreover, as a compounding quantity of a black pigment (C-1), the range of 10-100 mass parts per 100 mass parts of said carboxyl group-containing resin (A) is suitable. If the amount is too small, sufficient blackness cannot be obtained after firing, which is not preferable. On the other hand, when the amount is too large, the light transmittance is lowered, and an undercut is likely to occur.

(C-2) Silver powder Silver powder (C-2) used in the silver paste composition of the present invention imparts conductivity to the paste, and publicly known silver powder can be used, but Ag in an X-ray analysis pattern can be used. It is preferable from the viewpoint of firing properties that the half width of the (111) plane peak is 0.15 ° or more, preferably 0.19 ° or more. Silver powder (C-2) having a half width of less than 0.15 is preferable because the crystallinity of the silver powder is high and sintering between particles hardly occurs, and the resistance value does not decrease at a firing temperature of 620 ° C. or less. Absent. The half width is preferably 1.0 ° or less. If the half width exceeds 1.0 °, the degree of crystallinity of the silver powder is low, the binding between the particles proceeds too much, and there is a risk of irregular waviness or twisting of the line.

  Such silver powder (C-2) is generally produced by a method such as an atomizing method or a chemical reduction method. The atomization method is a method in which molten silver is sprayed with a fluid such as gas or water to obtain a silver powder. Spherical particles are easily obtained and is excellent in mass productivity. The chemical reduction method is a method for obtaining a silver powder by chemically reacting a water-soluble silver salt with a reducing agent. Specifically, silver nitrate is used as a water-soluble silver salt, metallic silver is precipitated using a base such as caustic alkali, ammonium salt, hydrazine as a reducing agent, and then the resulting silver slurry is washed with water and dried to obtain a silver powder. Is the way to get.

  The silver powder (C-2) thus obtained can be used in various shapes such as a sphere, flake shape, and dentrite shape, but a sphere shape is particularly used in consideration of optical characteristics and dispersibility. It is preferable.

  The silver powder (C-2) is an average particle diameter of 10 random silver powders observed at 10,000 times using an electron microscope (SEM), and is 0.1 to 5 μm, preferably 0.8. It is preferable to use one having a size of 4 to 2.0 μm. If this average particle size is less than 0.1 μm, light transmission is poor and it becomes difficult to draw a high-definition pattern. On the other hand, if the average particle size exceeds 5 μm, it is difficult to obtain line edge linearity. It is not preferable. In addition, it is preferable to use the thing of the magnitude | size of 0.5-3.5 micrometers in the average particle diameter measured with the micro track | truck.

Further, this silver powder (C-2) preferably has a specific surface area of 0.01 to 2.0 m ² / g, preferably 0.1 to 1.0 m ² / g. When this specific surface area is less than 0.01 m ² / g, sedimentation is likely to occur during storage. On the other hand, when the specific surface area exceeds 2.0 m ² / g, the oil absorption increases and the fluidity of the paste is impaired. It is not preferable.

  The amount of such silver powder (C-2) is preferably 50 to 90 parts by mass in 100 parts by mass of the silver paste composition. If the amount of silver powder is too small, sufficient conductivity of the conductive pattern obtained from such a paste cannot be obtained. On the other hand, if the amount is too large, the adhesion to the substrate is deteriorated.

(C-3) Other inorganic powders As the inorganic powder, black pigment and silver powder have been mentioned, but the present invention may include both black pigment and silver powder. In addition to these black pigments and silver powder, metals such as platinum, palladium, nickel, copper, aluminum, tin, lead, zinc, iron, iridium, osmium, rhodium, tungsten, molybdenum, ruthenium, etc., depending on the purpose and application Inorganic tin oxide such as tin oxide, indium oxide, and ITO (Indium Tin Oxide) can be blended together with or separately from the black pigment and silver powder.

(D) Compound having at least one radically polymerizable unsaturated group in one molecule As compound (D) having at least one radically polymerizable unsaturated group in one molecule used in the present invention, Hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate; mono- or di-glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol Acrylates; acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide, and N, N-dimethylaminopropylacrylamide; N, N-dimethylaminoethylamine Aminoalkyl acrylates such as acrylate, N, N-dimethylaminopropyl acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or their ethylene oxide adducts or Polyvalent acrylates such as propylene oxide adducts; Phenoxy acrylate, bisphenol A diacrylate, and acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; glycerin diglycidyl ether, glycerin triglycidyl ether, tri Aglycol ethers such as methylolpropane triglycidyl ether and triglycidyl isocyanurate Polyfunctional or monofunctional polyurethane acrylate that is an isocyanate modification of the above hydroxyalkyl acrylate; and melamine acrylate, and / or (meth) acrylates corresponding to the acrylate, and the like. A combination of the above can be used. Among these, compounds having at least two radically polymerizable unsaturated groups in one molecule, such as pentaerythritol triacrylate and dipentaerythritol hexaacrylate, are particularly preferable because of excellent photocurability.

  Hereinafter, this compound may be abbreviated as a polymerizable monomer.

  The blending amount of (D) having at least one radical polymerizable unsaturated group in one molecule is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). More preferably, the proportion is 10 to 70 parts by mass. If the blending amount is too small, the photocurability decreases, and pattern formation becomes difficult by alkali development after irradiation with active energy rays, which is not preferable. On the other hand, when the amount is too large, the solubility in an aqueous alkali solution is lowered, and the coating film becomes brittle.

(E-1) an oxime ester photopolymerization initiator represented by the general formula (I),
Examples of the photopolymerization initiator (E) used in the paste composition of the present invention include an oxime ester photopolymerization initiator (E-1 having a functional group represented by the above general formula (I) as a paste composition for LDI, for example. ). Specific examples of the oxime ester photopolymerization initiator include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) and the following general formula (VII)

2- (acetyloxyiminomethyl) thioxanthen-9-one is mentioned. Among these, the compound represented by the above formula (VII), 2- (acetyloxyiminomethyl) thioxanthen-9-one, is particularly preferable. A commercially available product is CGI-325 manufactured by Ciba Specialty Chemicals.

  As a compounding quantity of such a photoinitiator (E-1), the ratio of 0.1-1.0 mass% of the whole composition is preferable. Moreover, as a compounding quantity of such an oxime ester system photoinitiator (E-1), Preferably it is 0.01-20 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (A), More preferably Is a ratio of 0.01 to 5 parts by mass. If the amount of the oxime ester photopolymerization initiator (E-1) is too small relative to 100 parts by mass of the carboxyl group-containing resin (A), sufficient photocurability cannot be obtained, which is not preferable. On the other hand, if the amount is too large, the thick film curability is lowered and the cost of the product is increased, which is not preferable.

  In order to further increase the sensitivity of the paste composition of the present invention, it is preferable to blend a phosphine oxide photopolymerization initiator (E-2) containing a structure represented by the general formula (IV).

  As such a phosphine oxide photopolymerization initiator (E-2), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2 , 6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and the like.

  As a compounding quantity of such a phosphine oxide type photoinitiator (E-2), it is 60 mass parts or less with respect to 100 mass parts of said carboxyl group-containing resin (A), Preferably it is a ratio of 50 mass parts or less. is there. When the compounding quantity of a phosphine oxide type photoinitiator (E-2) exceeds 60 mass parts, since thick film curability falls and it leads to the cost increase of a product, it is unpreferable.

  Moreover, the compounding quantity of the oxime ester photoinitiator (E-1) represented by the said general formula (I) is the phosphine oxide type photoinitiator (E-2) represented by the said general formula (IV). It is preferable that the blending amount is at least equal to or less than the blending amount in order to obtain thick film curability with high sensitivity.

  The paste composition of the present invention can be used in combination with a known and commonly used photopolymerization initiator, if necessary. Specifically, benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-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- Aminoacetophenones such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 1-chloroanthracone Anthraquinones such as thiophene; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone Benzophenones; or xanthones; (2,6-dimethoxybenzoyl) -2,4,4-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6- Examples thereof include phosphine oxides such as trimethylbenzoyldiphenylphosphine oxide and ethyl-2,4,6-trimethylbenzoylphenyl phosphinate. In particular, thioxanthone photopolymerization initiators such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone, or bis (2,4,6-trimethylbenzoyl) -phenyl It is preferable to use a phosphine oxide photopolymerization initiator such as phosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide in view of deep curability.

  As a compounding quantity of such a thioxanthone type photoinitiator or a phosphine oxide type photoinitiator, with respect to 100 mass parts of said carboxyl group-containing resin (A), Preferably it is 30 mass parts or less, More preferably, it is 20 masses. It is a ratio of parts or less. If the blending amount of these thioxanthone photopolymerization initiators is too large, the thick film curability is lowered and the cost of the product is increased, which is not preferable.

(F) Sulfur compound represented by the above general formula By adding this sulfur compound, the sensitivity of the composition relating to active energy rays including laser light can be improved, but the present inventor presumes the reason as follows. ing. In the light irradiation site, as the radical polymerization reaction proceeds, it is difficult for the polymerizable monomer to diffuse, the polymerization rate and the reaction rate decrease, and the unreacted polymerizable monomer may remain. However, it is considered that by adding the sulfur compound (F) acting as a chain transfer agent, the polymerization reaction efficiently proceeds and the reaction rate is increased, and as a result, high sensitivity can be achieved.

(G) Boric acid Furthermore, it is preferable to add boric acid (G) to the paste composition of the present invention in order to increase the storage stability.

As such boric acid (G), an average particle size (D ₅₀ ) pulverized by a jet mill, a ball mill, a roll mill or the like is 20 μm or less, preferably 5 μm or less. The finely powdered product is likely to absorb moisture and re-aggregate, so that it is preferably used immediately after pulverization. Moreover, it can also grind | pulverize with resin, a solvent, etc. which are contained in a paste.

  The blending ratio of such boric acid (G) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the glass frit (B). Part. If the blending ratio of boric acid is too small with respect to 100 parts by mass of the glass frit (B), there is no effect of improving storage stability, which is not preferable.

  When boric acid (G) is blended in this way, it is necessary to use a hydrophobic solvent having a solubility in 100 g of water at 25 ° C. of 20 g or less. When an organic solvent having high solubility in water is used, water dissolved in the organic solvent ionizes the metal contained in the glass frit and causes gelation, which is not preferable.

(H) Phosphorus compound Furthermore, in order to further improve the storage stability of the paste composition of the present invention, the phosphorus compound (H) represented by the general formula (V) or the general formula (VI) may be added. preferable.

  Examples of such phosphorus compounds (H) include 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, diethyl phosphite, Dibutyl phosphate, dipropyl phosphite, diphenyl phosphite, isopropyl phosphite, diisopropyl phosphite, n-butyl-2-ethylhexyl hydroxyethylenediphosphonate, adenosine triphosphate, adenosine phosphate, mono ( 2-Methacryloyloxyethyl) acid phosphate, mono (2-acryloyl) Xylethyl) 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, Examples include 2-ethylhexyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, diethylene glycol acid phosphate, (2-hydroxyethyl) methacrylate acid phosphate, and the like. These phosphorus compounds can be used alone or in combination of two or more.

  As a compounding quantity of these phosphorus compounds (H), it is 10 mass parts or less with respect to 100 mass parts of said glass frit (B), Preferably, it is 0.1-5 mass parts. When the compounding amount of the phosphorus compound (H) exceeds 10 parts by mass with respect to 100 parts by mass of the glass frit (B), the calcination property is lowered, which is not preferable.

(Other compounds)
The paste composition of the present invention can use an organic solvent for the synthesis of the carboxyl group-containing resin (A), the adjustment of the composition, or the viscosity adjustment for application to a substrate or a carrier film. 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, di Glycol ethers such as propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate Acetic acid esters such as ethanol, propanol, ethylene glycol, propylene glycol Alcohols such as terpineol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha, which are used alone or in combination of two or more. be able to.

  If necessary, the paste composition of the present invention may be a known conventional thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, etc., or a known conventional polymer such as finely divided silica, organic bentonite, or montmorillonite. Blends known and commonly used additives such as thickeners, silicone-based, fluorine-based, polymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, etc. can do.

(Use of composition)
The paste composition of the present invention as described above is adjusted to a viscosity suitable for the coating method using, for example, the organic solvent, and on the substrate, the dip coating method, flow coating method, roll coating method, bar coater method, screen printing A tack-free coating film can be formed by applying the coating method by a method such as a coating method or a curtain coating method and drying it at about 60 to 120 ° C for about 5 to 40 minutes. Alternatively, a tack-free coating film can be formed by applying the above composition on a carrier film, drying it, and laminating it on a substrate.

  In addition, it is preferable from the surface of pattern formation property that the light absorbency per 1 micrometer of film thickness of the coating film dried in this way is 0.1-0.8.

  Then, the contact type (or non-contact type) is selectively exposed with active energy rays through a photomask having a pattern formed, and the unexposed portion is developed with a dilute alkaline aqueous solution (for example, 0.3 to 3% sodium carbonate aqueous solution). Thus, a black matrix pattern and a conductive pattern are formed.

  As the exposure apparatus used for the active energy ray irradiation, a direct drawing apparatus (for example, a laser direct imaging apparatus for directly drawing an image with a laser using CAD data from a computer) can be used. Examples of the active energy ray source include a laser diode that emits laser light having a maximum wavelength in the range of 350 nm to 420 nm, a gas laser, a solid laser, and the like, and a laser diode is particularly preferable.

  As the direct drawing apparatus, for example, those manufactured by Nippon Orbotech, Pentax, Hitachi Via Mechanics, Ball Semiconductor, etc. can be used, and any apparatus may be used.

  In addition to the direct drawing apparatus, a conventional exposure machine can be used. As the 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.

  For the development, a spray method, a dipping method or the like is used. Developers include aqueous metal alkali solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium silicate, and aqueous amine solutions such as monoethanolamine, diethanolamine, triethanolamine, and tetramethylammonium hydroxide. A dilute alkaline aqueous solution having a concentration of 1.5% by mass or less is preferably used, but the carboxyl group of the carboxyl group-containing resin (A) in the composition is saponified and the uncured part (unexposed part) is removed. The developer is not limited to the developer as described above. Further, it is preferable to perform washing with water and acid neutralization in order to remove unnecessary developer after development.

  The substrate patterned by the above development can be baked at about 400 to 600 ° C. in air or in a nitrogen atmosphere to form a desired pattern such as a black matrix pattern or a conductive pattern.

  EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

Synthesis Example 1: Synthesis of carboxyl group-containing resin In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, methyl methacrylate and methacrylic acid were charged at a molar ratio of 0.87: 0.13 as a solvent. Dipropylene glycol monomethyl ether and azobisisobutyronitrile as a catalyst were added and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere to obtain a carboxyl group-containing resin solution. This resin had a weight average molecular weight of about 10,000 and an acid value of 74 mgKOH / g. In addition, the measurement of the weight average molecular weight of the obtained copolymer resin is Shimadzu Corporation pump LC-6AD, Showa Denko Co., Ltd. column Shodex (trademark) KF-804, KF-803, KF-802. Was measured by high performance liquid chromatography. Hereinafter, this carboxyl group-containing resin solution is referred to as A-1 varnish.

Synthesis Example 2: Synthesis of carboxyl group-containing photosensitive resin In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, the charge ratio of methyl methacrylate and methacrylic acid was adjusted to 0.76: 0.24 in molar ratio. Dipropylene glycol monomethyl ether as a solvent and azobisisobutyronitrile as a catalyst were added and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere to obtain a carboxyl group-containing resin solution. This carboxyl group-containing resin solution is cooled, methylhydroquinone is used as a polymerization inhibitor, tetrabutylphosphonium bromide is used as a catalyst, and glycidyl methacrylate is added at 95 to 105 ° C. for 16 hours with respect to 1 mol of carboxyl groups of the resin. The addition reaction was carried out at an addition molar ratio of 0.12 mol, and the mixture was taken out after cooling. The weight average molecular weight of the carboxyl group-containing photosensitive resin produced by the above reaction was about 10,000, the acid value was 59 mgKOH / g, and the double bond equivalent was 950. Hereinafter, this carboxyl group-containing photosensitive resin solution is referred to as A-2 varnish.

[Pattern formation by direct drawing device using black paste]
Examples 1 to 9 and Comparative Example 1
The compounding components shown in Table 1 using the A-1 varnish and A-2 varnish obtained in Synthesis Examples 1 and 2 were kneaded with a three-roll mill to obtain a black paste composition.

The black paste compositions of Examples 1 to 9 and Comparative Example 1 were applied to the entire surface of the glass substrate using a 300 mesh polyester screen. Next, it dried for 20 minutes at 90 degreeC using the hot-air circulation type drying furnace, and formed the film | membrane with favorable touch-drying property. Next, using a striped CAD data having a line width of 100 μm and a space width of 150 μm, a laser direct imaging exposure apparatus (DI-μ10 manufactured by Pentax) having a blue-violet laser having a central wavelength of 405 nm as a light source, It exposed so that the integrated light quantity on a composition might be 40 mJ / cm < ² >. Thereafter, development was carried out for 20 seconds using a 0.4 wt% Na ₂ CO ₃ aqueous solution having a liquid temperature of 30 ° C., followed by washing with water. Finally, it was fired in air using an electric furnace.

  The firing was performed by raising the temperature from room temperature to 590 ° C. at a rate of 5 ° C./min, holding at 590 ° C. for 10 minutes, and then allowing to cool to room temperature.

  Table 2 shows the results of the evaluation of various characteristics of the substrates thus obtained.

  The evaluation methods in Table 2 are as follows.

(1) Measurement of absorbance The absorbance of an evaluation substrate in which a coating film having a dry film thickness of 5 μm and 10 μm was formed on soda lime glass was measured using an ultraviolet-visible spectrophotometer. From the obtained data, the absorbance per 1 μm thickness at 405 nm was calculated.

(2) Evaluation of Laser Photosensitivity A line of L / S = 100/150 μm is exposed with an integrated light quantity of 50 mJ / cm ^{2 and} developed for 20 seconds using a 0.4 wt% Na ₂ CO ₃ aqueous solution with a liquid temperature of 30 ° C. And evaluated whether a line could be formed with an optical microscope. The evaluation criteria are as follows.
○: No defect is observed at all.
Δ: Some defects are observed.
X: A line cannot be formed.
(3) Calculation of minimum exposure amount Exposure was performed by changing the integrated light amount, and the minimum exposure amount that could form a line of L / S = 100/150 μm without a defect was measured. Since the comparative example was not practical because the exposure time with a laser was long, the subsequent test was not performed.

(4) Line shape after pattern formation The pattern after development in the alkali development type black paste composition when exposed at the above minimum exposure amount is observed with a microscope, and there is no irregular variation in the line. It evaluated by whether there was no etc. The evaluation criteria are as follows.
○: There is no irregular variation and there is no twist.
(Triangle | delta): There are some irregular variations, a twist, etc.
X: Irregular variation, warping, etc.
(5) Line shape after firing The line shape after firing was evaluated by observing a pattern that had been finished up to firing with a microscope, and whether the lines had irregular irregularities and were not twisted. The evaluation criteria are as follows.
○: There is no irregular variation and there is no twist.
(Triangle | delta): There are some irregular variations, a twist, etc.
X: Irregular variation, warping, etc.
(6) Adhesiveness Adhesiveness was evaluated by peeling with a cellophane pressure-sensitive adhesive tape and checking for pattern peeling. The evaluation criteria are as follows.
○: No pattern peeling.
Δ: There is a slight pattern peeling.
X: The pattern peels frequently.

  As is clear from the results shown in Table 2, it can be seen that the black paste composition of the present invention has sufficient sensitivity to laser light and can form a high-definition pattern. Furthermore, there was no irregular variation in the line shape after firing, and the adhesion to the substrate was excellent.

  The blackness after firing was satisfactory, and the storage stability was excellent.

[Pattern formation with a direct writing apparatus using a silver paste composition]
Examples 10 to 18 and Comparative Example 2
The compounding components shown in Table 3 using the A-1 varnish and A-2 varnish obtained in Synthesis Examples 1 and 2 were kneaded with a three-roll mill to obtain a silver paste composition.

The silver paste compositions of Examples 10 to 18 and Comparative Example 2 were used and applied to the entire surface of a glass substrate using a 300 mesh polyester screen. Next, it dried for 20 minutes at 90 degreeC using the hot-air circulation type drying furnace, and formed the film | membrane with favorable touch-drying property. Next, using a striped CAD data having a line width of 50 μm and a space width of 200 μm, a laser direct imaging exposure apparatus (DI-μ10 manufactured by Pentax) having a blue-violet laser having a central wavelength of 405 nm as a light source, It exposed so that the integrated light quantity on a composition might be 40 mJ / cm <2>. Thereafter, development was carried out for 20 seconds using a 0.4 wt% Na ₂ CO ₃ aqueous solution having a liquid temperature of 30 ° C., followed by washing with water. Finally, it was fired in air using an electric furnace.

  The firing was performed by raising the temperature from room temperature to 590 ° C. at a rate of 5 ° C./min, holding at 590 ° C. for 10 minutes, and then allowing to cool to room temperature.

  Table 4 shows the results of the evaluation of various characteristics of the substrates thus obtained.

  In addition, among the evaluation methods in Table 4, (1) measurement of absorbance, (4) line shape after pattern formation, (5) line shape after firing, and (6) adhesion are the above Examples 1 to 9. The same as Comparative Example 1. However, (2) evaluation of laser photosensitivity, (3) calculation of minimum exposure amount, and (7) measurement of specific resistance value were performed as follows.

(2) Evaluation of Laser Photosensitivity A line of L / S = 50/200 μm is exposed with an integrated light quantity of 50 mJ / cm ^{2 and} developed for 20 seconds using a 0.4 wt% Na ₂ CO ₃ aqueous solution with a liquid temperature of 30 ° C. And evaluated whether a line could be formed with an optical microscope. The evaluation criteria are as follows.

  ○: No defect is observed at all.

  Δ: Some defects are observed.

  X: A line cannot be formed.

(3) Calculation of minimum exposure amount Exposure was performed by changing the integrated light amount, and the minimum exposure amount that could form a line of L / S = 50/200 μm without a defect was measured. Since the comparative example was not practical because the exposure time with a laser was long, the subsequent test was not performed.

(7) Measurement substrate for specific resistance value A test substrate was prepared in the same manner as in the above (line shape after firing) except that exposure was performed using CAD data having a pattern size of 0.4 cm × 10 cm. For the test substrate thus obtained, the resistance value of the fired film was measured using a milliohm high tester, and then the film thickness of the fired film was measured using a surf coater to calculate the specific resistance value of the fired film.

  As is apparent from the results shown in Table 4, it can be seen that the alkali development type silver paste composition of the present invention has sufficient sensitivity to laser light and can form a high-definition pattern. Furthermore, there was no irregular variation in the line shape after firing, the specific resistance value was sufficient as an electrode material, the adhesion to the substrate was good, and the storage stability was excellent.

[Pattern formation by lamp-type exposure using black paste composition]
The alkali development type black paste compositions of Examples 1 to 9 and Comparative Example 1 were applied to the entire surface of a glass substrate using a 300 mesh polyester screen. Next, it dried for 20 minutes at 90 degreeC using the hot-air circulation type drying furnace, and formed the film | membrane with favorable touch-drying property. Next, using a glass dry plate on which a striped negative pattern having a line width of 100 μm and a space width of 150 μm is formed as a photomask, an exposure apparatus (MAT-5301 manufactured by Hakutosha Co., Ltd.) equipped with an ultrahigh pressure mercury lamp as a light source The total amount of light was exposed to 50 mJ / cm ² . Thereafter, development was carried out for 20 seconds using a 0.4 mass% Na ₂ CO ₃ aqueous solution having a liquid temperature of 30 ° C., followed by washing with water. Finally, it was fired in air using an electric furnace.

  The firing was performed by raising the temperature from room temperature to 590 ° C. at a rate of 5 ° C./min, holding at 590 ° C. for 10 minutes, and then allowing to cool to room temperature.

Table 5 shows the results of evaluating the various characteristics of the substrates thus obtained. In addition, the evaluation method in Table 5 is the same as the case of the said Examples 1-9 and the comparative example 1 (however, the light absorbency is not measured in this Example and a comparative example).

  As is apparent from the results shown in Table 5, it can be seen that the alkali development type black paste composition of the present invention has sufficient sensitivity even when an ultrahigh pressure mercury lamp is used as the light source and can form a high-definition pattern. It was.

[Pattern formation by lamp-type exposure using silver paste composition]
The alkali development type silver paste compositions of Examples 10 to 18 and Comparative Example 2 were used and applied to the entire surface using a 300-mesh polyester screen on a glass substrate. Next, it dried for 20 minutes at 90 degreeC using the hot-air circulation type drying furnace, and formed the film | membrane with favorable touch-drying property. Next, using a glass dry plate on which a striped negative pattern having a line width of 50 μm and a space width of 200 μm is formed as a photomask, an exposure apparatus (MAT-5301 manufactured by Hakutosha Co., Ltd.) equipped with an ultrahigh pressure mercury lamp as a light source The total amount of light was exposed to 40 mJ / cm ² . Thereafter, development was carried out for 20 seconds using a 0.4 mass% Na ₂ CO ₃ aqueous solution having a liquid temperature of 30 ° C., followed by washing with water. Finally, it was fired in air using an electric furnace.

  The firing was performed by raising the temperature from room temperature to 590 ° C. at a rate of 5 ° C./min, holding at 590 ° C. for 10 minutes, and then allowing to cool to room temperature.

Table 6 shows the results of evaluation of various properties of the substrates thus obtained. In addition, the evaluation method in Table 6 is the same as the case of the said Examples 10-18 (however, in this Example and a comparative example, the measurement of an absorbance and the measurement of a specific resistance value are not carried out).

  As is apparent from the results shown in Table 6, it can be seen that the alkali development type silver paste composition of the present invention has sufficient sensitivity even when an ultrahigh pressure mercury lamp is used as the light source, and can form a high-definition pattern. It was.

[Pattern formation by lamp-type exposure using black silver paste composition]
Examples 19 to 26 and Comparative Example 3
The compounding components shown in Table 7 using the A-1 varnish and A-2 varnish obtained in the above synthesis example were kneaded with a three-roll mill to obtain an alkali developing type black silver paste composition.

An alkali development type black silver paste composition containing both a black pigment and silver powder as an inorganic component was also evaluated. The black silver paste compositions of Examples 19 to 26 and Comparative Example 3 were applied to the entire surface using a 300-mesh polyester screen on a glass substrate. Next, it dried for 20 minutes at 90 degreeC using the hot-air circulation type drying furnace, and formed the film | membrane with favorable touch-drying property. Next, using a glass dry plate on which a striped negative pattern having a line width of 50 μm and a space width of 200 μm is formed as a photomask, an exposure apparatus (MAT-5301 manufactured by Hakutosha Co., Ltd.) equipped with an ultrahigh pressure mercury lamp as a light source The total amount of light was exposed to 40 mJ / cm ² . Thereafter, development was carried out for 20 seconds using a 0.4 mass% Na ₂ CO ₃ aqueous solution having a liquid temperature of 30 ° C., followed by washing with water. Finally, it was fired in air using an electric furnace.

  The firing was performed by raising the temperature from room temperature to 590 ° C. at a rate of 5 ° C./min, holding at 590 ° C. for 10 minutes, and then allowing to cool to room temperature.

Table 8 shows the results of the evaluation of various characteristics of the substrates thus obtained. The evaluation methods in Table 8 are the same as those in Examples 10 to 18 and Comparative Example 2.

  As is apparent from the results shown in Table 8, it was found that the alkali development type black silver paste composition of the present invention has sufficient sensitivity and can form a high-definition pattern.

Claims (15)

(A) carboxyl group-containing resin, (B) glass frit, (C) inorganic powder, (D) a compound having at least one radical polymerizable unsaturated group in one molecule, and (E-1) the following general An oxime ester photopolymerization initiator having a functional group represented by the formula (I),

In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
And (F) a sulfur compound represented by the following general formula (II)

(In the formula, R ³ represents an alkyl group, an aryl group or a substituted aryl group, R ⁴ represents a hydrogen atom or an alkyl group, and R ³ and R ⁴ are bonded to each other to form an oxygen, sulfur and nitrogen atom. (A group of nonmetallic atoms necessary to form a 5-membered to 7-membered ring which may contain a selected heteroatom.)
An alkali-developable paste composition comprising: The oxime ester photopolymerization initiator according to claim 1, wherein the oxime ester photopolymerization initiator (E-1) is represented by the following general formula (III).

(In the formula, one or two R ⁵ are represented by the following general formula (I) (provided that when two R ⁵ are represented by the general formula (I), R ⁵ is different from each other)). The remaining R ⁵ represents a hydrogen atom, a methyl group, a phenyl group, or a halogen atom (provided that each R ⁵ is different).

In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
The alkali-developable paste composition according to claim 1, wherein The alkali development type according to claim 1 or 2, wherein the carboxyl group-containing resin (A) is a carboxyl group-containing resin further having (A-1) one or more radically polymerizable unsaturated groups. Paste composition. Furthermore, (E-2) a phosphine oxide photopolymerization initiator containing a structure represented by the following general formula (IV)

(Wherein R ⁶ and R ⁷ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or a halogen atom, an alkyl group or an alkoxy group. A substituted aryl group, or either one represents a carbonyl group having 1 to 20 carbon atoms.)
The alkali development type paste composition according to any one of claims 1 to 3, further comprising: The composition according to claim 4, wherein the amount of the oxime ester photopolymerization initiator (E-1) represented by the general formula (I) is a phosphine oxide light represented by the general formula (IV). An alkali developing paste composition characterized by being less than the blending amount of the polymerization initiator (E-2). Furthermore, (G) boric acid is contained, The alkali development type paste composition as described in any one of Claims 1 thru | or 5 characterized by the above-mentioned. Furthermore, (H) a phosphorus compound represented by the following general formula (V) or general formula (VI)

The alkali development type paste composition according to any one of claims 1 to 6, wherein the paste composition is an alkali development type paste composition.   The compounding quantity of the compound (E-1) represented by the said general formula (I) is 0.1-1.0 mass% of the whole composition quantity, The any one of Claims 1 thru | or 7 characterized by the above-mentioned. Item 4. An alkali development type paste composition according to Item.   The alkali developing paste composition according to any one of claims 1 to 8, wherein the (C) inorganic powder is (C-1) a black pigment. The alkali developing paste composition according to any one of claims 1 to 8, wherein the (C) inorganic powder is (C-2) silver powder. An alkali developing type, wherein the coating film obtained by coating and drying the composition according to any one of claims 1 to 10 has an absorbance per 1 μm of film thickness of 0.1 to 0.8. Paste composition. A method of forming a pattern using the composition according to any one of claims 1 to 11,
(1) A pattern drawing process using an active energy ray having a maximum wavelength of 350 nm to 420 nm;
(2) a step of selectively forming a pattern by developing with a dilute alkaline aqueous solution;
(3) a step of firing at 400 to 600 ° C .;
A method of forming a pattern, comprising: 13. The pattern forming method according to claim 12, wherein the pattern is a black matrix pattern and / or a conductive pattern. A pattern obtained by the pattern forming method according to claim 12. A plasma display panel comprising the pattern according to claim 14.