KR20080044184A - Alkali development type paste composition, method for conductive pattern and black matrix pattern formation using the same, and the conductive pattern and the black matrix pattern - Google Patents

Abstract

An alkali development type paste composition is provided to ensure high sensitivity to actinic energy rays and to be useful for forming a precise micropattern efficiently. An alkali development type paste composition includes (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 a molecule, (E) an oxime-based photopolymerization initiator represented by the following formula 1, and (F) a sulfur compound represented by the following formula 2. In the formula 1, R^1 represents a hydrogen atom, C1-6 alkyl group, or phenyl group, R^2 represents a hydrogen atom or C1-6 alkyl group. In the formula 2, R^3 represents an alkyl group, aryl group, or substituted aryl group, R^4 represents a hydrogen atom or alkyl group, and R^3 and R^4 represent a non-metallic atom group and are bonded to each other to form a 5-membered to 7-membered ring with or without a hetero atom selected from oxygen, sulfur, and nitrogen atoms.

Description

Alkali development type paste composition, and the method of forming a black matrix pattern using the alkali-developing paste composition, and the conductive pattern and the black matrix pattern using the same, and the conductive pattern and the black matrix pattern therefor {ALKALI DEVELOPMENT TYPE PASTE COMPOSITION, METHOD FOR CONDUCTIVE PATTERN AND BLACK MATRIX PATTERN AND THE BLACK MATRIX PATTERN}

[Patent Document 1] Japanese Unexamined Patent Publication No. 2002-351071 (Patent Claims)

[Patent Document 2] Japanese Unexamined Patent Publication No. 2002-351072 (Patent Claims)

[Patent Document 3] Japanese Unexamined Patent Application Publication No. 2004-45596 (Patent Claims)

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkali developing paste composition suitable for forming a conductive pattern and a black matrix pattern useful for a thin display and the like, a method of forming a conductive pattern and a black matrix pattern using the same, and a conductive pattern and a black matrix pattern thereof. In addition, below, when both a conductive pattern and a black matrix pattern are indicated, it shows as a pattern. In cases other than this, it displays as a conductive pattern and a black matrix pattern, respectively. More specifically, the present invention is suitable for a laser direct imaging apparatus using an active energy ray having a maximum wavelength of 350 nm to 420 nm, is useful for efficiently forming a precise and fine pattern, and is an alkali phenomenon having excellent storage stability. It relates to a paste composition of a mold, a method of forming a pattern using the same, and the pattern.

Conventionally, the electroconductive pattern is formed in the glass substrate of a thin display, etc. as an electrode. In addition, a black matrix pattern is used for the front panel. And the formation method is, for example, by applying a pattern resist on a glass substrate and drying it to form a coating film, and exposing the image using an active energy ray through a photomask in which a circuit or an electrode pattern is drawn on the coating film, and then exposing the exposed portion. By developing with an aqueous alkali solution using the difference in solubility in the developer of the non-exposed part, the resist layer corresponding to the circuit and the electrode pattern was formed and fired to form a pattern in close contact with the glass substrate.

As a composition which is exposed and exposed by the laser scanning using this active energy ray, the composition containing a specific dye sensitizer, a titanocene compound, etc. (for example, refer patent document 1 and patent document 2), or specific bisacyl Although laser photosensitive compositions containing phosphine oxides (see Patent Document 3, for example) have been proposed, sufficient sensitivity to active energy rays has not been obtained in these compositions.

The present invention was developed in view of the above problems, and its main object is an alkali developing paste composition useful for efficiently forming a precise and fine pattern with high sensitivity to active energy rays, a method of forming a pattern using the same, and Is to provide that pattern.

In order to solve the said subject, this invention is equipped with the following structures.

(1) (A) carboxyl group-containing resin, (B) glass frit, (C) inorganic powder, (D) compound which has at least 1 radically polymerizable unsaturated group in 1 molecule, (E-1) represented by following General formula (1) An alkali developing type paste composition comprising an oxime-based photopolymerization initiator and (F) a sulfur compound represented by the following general formula (2).

(In formula, R <^1> represents a hydrogen atom, a C1-C6 alkyl group, or a phenyl group, R <^2> represents a hydrogen atom, a C1-C6 alkyl group.)

(Wherein 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 may combine with each other to include a hetero atom selected from oxygen, sulfur and nitrogen atoms) Represents a group of nonmetallic atoms needed to form a 5 to 7 membered ring)

(2) The alkali-developing paste composition according to the above (1), wherein the oxime photoinitiator (E-1) is an oxime photoinitiator represented by the following formula (3).

(Wherein one or two R ⁵ is represented by the following formula (1), provided that when two R ⁵ is represented by the formula (1), R ⁵ is different from each other), and the remaining R ⁵ is a hydrogen atom , Methyl, phenyl or halogen atom (where each R ⁵ is different)

<Formula 1>

(In formula, R <^1> represents a hydrogen atom, a C1-C6 alkyl group, or a phenyl group, R <^2> represents a hydrogen atom, a C1-C6 alkyl group.)

(3) The alkali developing type according to the above (1) or (2), wherein the carboxyl group-containing resin (A) is a carboxyl group-containing resin having (A-1) one or more radically polymerizable unsaturated groups. Paste composition.

(4) The alkali-developing paste composition according to (1) or (2), further comprising (E-2) a phosphine oxide-based photoinitiator represented by the following general formula (4).

(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 an aryl group substituted with a halogen atom, an alkyl group or an alkoxy group, Or any one represents a carbonyl group having 1 to 20 carbon atoms)

(5) The compounding quantity of the oxime type photoinitiator (E-1) represented by the said General formula (1) in (4) is larger than the compounding quantity of the phosphine oxide type photoinitiator (E-2) represented by the said General formula (4). Alkali developing paste composition characterized by few.

(6) The alkali-developing paste composition according to (1) or (2), further comprising (G) boric acid.

(7) The alkali-developing paste composition according to the above (1) or (2), further comprising (H) a phosphorus compound represented by the following general formula (5) or (6).

(8) The alkali-developing paste composition according to any one of (1) to (7), wherein the absorbance is 0.1 to 0.8 per 1 µm of the film thickness of the coating film coated with the composition.

(9) The alkali-developing paste composition according to (1) or (2), wherein the inorganic powder (C) is a black pigment, silver powder, or both.

(10) It is a formation method of the pattern using the composition in any one of said (1)-(9),

(1) a step of pattern exposing with an active energy ray,

(2) process of forming pattern selectively by developing with dilute aqueous alkali solution,

(3) step of baking at 400 to 600 ° C

Forming method of a pattern comprising a.

(11) The method for forming a pattern according to (10), wherein the active energy ray is a laser oscillation light source or a lamp light source.

(12) The pattern obtained by the formation method of the pattern as described in said (10) or (11).

(13) The pattern according to (12), wherein the pattern is a conductive pattern.

(14) The pattern according to (12) or (13), wherein the pattern includes a black matrix pattern.

(15) A plasma display panel comprising a pattern formed of the alkali developing paste composition according to any one of (1) to (9).

(16) A plasma display panel comprising the pattern according to any one of (12) to (14).

(17) The alkali developing type according to the above (1) or (2), wherein the compounding amount of the oxime photoinitiator (E-1) represented by the formula (1) is 0.1 to 1.0 mass% of the total amount of the composition. Paste composition.

Best Mode for Carrying Out the Invention

The alkali-developing paste composition of the present invention is a compound having one or more radically polymerizable unsaturated groups in (A) carboxyl group-containing resin, (B) glass frit, (C) inorganic powder, (D) one molecule, (E-1 ) It contains the oxime system photoinitiator represented by the said Formula (1), and (F) the sulfur compound represented by the said Formula (2), and has the characteristic that it shows the outstanding photocurability with respect to an active energy ray.

Moreover, in a preferable aspect, the said composition contains (G) boric acid, and the composition excellent in storage stability can be provided. Moreover, the composition containing the (H) phosphorus compound and excellent in storage stability can be provided.

Hereinafter, each structural component of the alkali developing type paste composition of this invention is demonstrated in detail.

(A) carboxyl group-containing resin

As carboxyl group-containing resin (A) contained in the alkali developing type paste composition of this invention, the well-known conventional resin compound which contains a carboxyl group in a molecule | numerator can be used.

Specifically, resin listed below is mentioned.

(1) carboxyl group-containing resin obtained by copolymerizing unsaturated carboxylic acid, such as (meth) acrylic acid, and one or more types of compounds which have an unsaturated double bond other than that,

(2) Glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl to a copolymer of unsaturated carboxylic acids such as (meth) acrylic acid and one or more kinds of compounds having an unsaturated double bond other than that Carboxyl group-containing photosensitive resin obtained by adding an ethylenically unsaturated group as a pendant by the compound which has unsaturated double bond, such as (meth) acrylate, and (meth) acrylic acid chloride, etc.,

(3) A copolymer 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 Carboxyl group-containing photosensitive resin obtained by making unsaturated carboxylic acid, such as (meth) acrylic acid, react, and making polybasic acid anhydride react with the produced | generated secondary hydroxyl group,

(4) A hydroxyl group, such as 2-hydroxyethyl (meth) acrylate, and an unsaturated double bond are added 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. Carboxyl group-containing photosensitive resin obtained by making compound which has

(5) a carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting a produced hydroxyl group with a saturated or unsaturated polybasic anhydride;

(6) A hydroxyl group and a carboxyl group-containing photosensitive resin obtained by reacting a saturated or unsaturated polybasic acid anhydride with a hydroxyl group-containing polymer such as a polyvinyl alcohol derivative, and then reacting the resulting carboxylic acid with a compound having an epoxy group and an unsaturated double bond in one molecule. ,

(7) A saturated or unsaturated polybasic anhydride is added to a reaction product of a polyfunctional epoxy compound, an unsaturated monocarboxylic acid, and a compound having at least one alcoholic hydroxyl group in one molecule and one reactive group other than the alcoholic hydroxyl group reacting with the epoxy group. Carboxyl group-containing photosensitive resin obtained by making it react,

(8) Carboxyl group content obtained by making unsaturated monocarboxylic acid react with the polyfunctional oxetane compound which has two or more oxetane rings in 1 molecule, and making a saturated or unsaturated polybasic acid anhydride react with the primary hydroxyl group in the obtained modified oxetane resin. Photosensitive resin, and

(9) After reacting unsaturated monocarboxylic acid with a polyfunctional epoxy resin, a compound having one oxirane ring and at least one ethylenically unsaturated group is further reacted with a carboxyl group-containing resin obtained by reacting a polybasic anhydride. Although carboxyl group-containing photosensitive resin obtained etc. are mentioned, It is not limited to this.

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

In addition, in this specification, (meth) acrylate is a term which generically mentions acrylate, methacrylate, and mixtures thereof, and the same also about other similar expression.

Since the carboxyl group-containing resin (A) mentioned above has many free carboxyl groups in the side chain of a backbone polymer, image development by dilute alkali aqueous solution is attained.

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 part by the developing solution proceeds, so that the line dries out more than necessary, and in some cases, the exposed part. It is not preferable because it is difficult to draw a normal resist pattern by dissolving and peeling with a developer without distinguishing between the unexposed portion and the unexposed portion.

Moreover, although the weight average molecular weight of the said carboxyl group-containing resin (A) changes with resin frame | skeleton, it is preferable to exist in the range of 2,000-150,000 generally and 5,000-100,000. If the weight average molecular weight is less than 2,000, the tack-free performance may deteriorate, the moisture resistance of the post-exposure coating film may deteriorate, and a film reduction may occur at the time of development, and the resolution may be greatly reduced. On the other hand, when a weight average molecular weight exceeds 150,000, developability may become remarkably bad and storage stability may be inferior.

When the compounding quantity of such carboxyl group-containing resin (A) uses (C-1) black pigment as (C), it is 10-80 mass% in the whole composition, More preferably, it is 15-50 mass%. Moreover, when (C-2) silver powder is used as (C), Preferably it is 2-50 mass%, More preferably, it is 4-30 mass%. If the amount is too small, the coating film strength is lowered, which is not preferable. On the other hand, when too much, since viscosity becomes high and applicability | paintability etc. fall, it is unpreferable.

(B) glass frit

As the glass frit (B) used for the alkali-developing paste composition of the present invention, a low melting glass frit having a softening point of 300 to 600 ° C is used, and preferably containing lead oxide, bismuth oxide, or zinc oxide as a main component. Can be used. Moreover, it is preferable to use the thing of 20 micrometers or less of average particle diameters from the viewpoint of the resolution, Preferably it is 5 micrometers or less. Preferred examples of the glass powder mainly containing lead oxide is a PbO as the oxide-based mass%, 48 to 82%, B ₂ O ₃ is 0.5 to 22%, SiO ₂ is from 3 to 32%, Al ₂ O ₃ is 0 To 12%, BaO is 0 to 10%, ZnO is 0 to 15%, TiO ₂ is 0 to 2.5%, Bi ₂ O ₃ is 0 to 25%, and has a softening point of 420 to 590 ° C. Can be mentioned.

Further, preferable examples of the glass powder mainly containing bismuth oxide is, as the oxide-based mass% Bi ₂ O ₃ is 35 to 88%, B ₂ O ₃ 5 to 30%, SiO ₂ 0 to 20%, Al Amorphous frits having a composition having 0 to 5% of ₂ O ₃ , 1 to 25% of BaO and 1 to 20% of ZnO, and having a softening point of 420 to 590 ° C.

Moreover, as a preferable example of the glass powder which has zinc oxide as a main component, ZnO is 25 to 60%, K ₂ O is 2 to 15%, B ₂ O ₃ is 25 to 45%, and SiO ₂ is the mass% on the basis of oxide. An amorphous frit having a composition having 1 to 7%, Al ₂ O ₃ of 0 to 10%, BaO of 0 to 20%, and MgO of 0 to 10%, and having a softening point of 420 to 590 ° C.

The compounding quantity of such glass frit becomes like this. Preferably it is 1-20 mass% in the whole composition, More preferably, it is 2-10 mass%. When there is too little compounding quantity, adhesiveness with a base material will fall, and when there is too much compounding quantity, there exists a possibility of causing thickening and gelation of a composition. Moreover, when forming a conductive pattern, there exists a possibility that it may raise the specific resistance value after baking, and neither is preferable.

(C) inorganic powder

The (C) inorganic powder used for the alkali developing type paste composition of this invention contains a black pigment (C-1) or silver powder (C-2).

Black Pigment (C-1)

As a black pigment (C-1) of the component (C) used for the alkali-developing paste composition of this invention, metal oxide and / or metal element of individual, such as Cu, Fe, Cr, Mn, Co, Ru, La, etc. The composite oxide containing 2 or more types can be used preferably. 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 viewpoint of blackness, the average particle diameter is preferably 1.0 µm or less, more preferably 0.6 µm or less.

Among these black pigments, it is particularly preferable to use cobalt trioxide (Co ₃ O ₄ ) fine particles having a specific surface area in the range of 1.0 to 20 m 2 / g. The reason is that, when the specific surface area is less than 1.0 m 2 / g, the precision of pattern formation by exposure decreases, and it becomes difficult to obtain the linearity of a line edge or the plastic film of sufficient inspection. On the other hand, when it exceeds 20 m <2> / g, the surface area of particle | grains becomes large too much and it becomes easy to produce an undercut at the time of image 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 too small, sufficient guminess cannot be obtained after firing, which is not preferable. On the other hand, when too much, since light transmittance falls and it becomes easy to produce an undercut, it is unpreferable.

Silver powder (C-2)

The silver powder (C-2) of the component (C) used in the alkali-developing paste composition of the present invention imparts conductivity to the paste, and although a conventionally known silver powder can be used, Ag (111) in the X-ray analysis pattern is used. It is preferable from the viewpoint of plasticity that the half width of a) peak is 0.15 ° or more, preferably 0.19 ° or more. In silver powder (C-2) whose half width is less than 0.15, since the crystallinity degree of silver powder is high and sintering between particle | grains arises, since resistance value does not fall at the baking temperature below 620 degreeC, it is unpreferable. Moreover, it is preferable that the said half width is 1.0 degrees or less. When the half width exceeds 1.0 °, the crystallinity of the silver powder is low, and the binding between particles is excessively advanced, which may cause irregular bending and torsion of the line.

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

The silver powder (C-2) obtained in this way can have various shapes, such as spherical shape, a flake shape, and a dendrite shape, but it is preferable to use a spherical thing especially in consideration of optical characteristics and dispersibility. In addition, this silver powder (C-2) uses the thing of the size of 0.1-5 micrometers, Preferably it is 0.4-2.0 micrometers with the average particle diameter of ten random silver powders observed 10,000 times using the electron microscope (SEM). desirable. When this average particle diameter is less than 0.1 micrometer, light transmittance worsens and it is difficult to draw a high precision fine pattern, and when the average particle diameter exceeds 5 micrometers, since the linearity of a line edge becomes difficult, it is unpreferable. In addition, it is preferable to use the thing of the magnitude | size of 0.5-3.5 micrometers as an average particle diameter measured by the microtrack.

Moreover, it is preferable to use this silver powder (C-2) whose specific surface area is 0.01-2.0 m <2> / g, Preferably it is 0.1-1.0 m <2> / g. When the specific surface area is less than 0.01 m 2 / g, it is easy to cause sedimentation during storage, while when the specific surface area exceeds 2.0 m 2 / g, it is not preferable because the oil absorption amount is large and the fluidity of the paste is impaired.

Preferably the compounding quantity of such silver powder (C-2) is 50-90 mass parts with respect to 100 mass parts of alkali developing paste compositions. When the compounding quantity of silver powder is too small, sufficient electroconductivity of the electroconductive pattern obtained from such a paste will not be obtained, and when too large, since adhesiveness with a base material will worsen, it is unpreferable.

(D) a compound having at least one radical polymerizable unsaturated group in one molecule

As a compound (D) which has at least 1 or more radically polymerizable unsaturated group in the said 1 molecule used for this invention, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, dipenta Hydroxyalkyl acrylates such as erythritol pentaacrylate; Mono or diacrylates of glycols such as ethylene glycol, methoxy tetraethylene glycol, polyethylene glycol and propylene glycol; Acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide and N, N-dimethylaminopropylacrylamide; Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; Polyhydric acrylates such as polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or ethylene oxide adducts or propylene oxide adducts thereof; Acrylates such as phenoxyacrylate, bisphenol A diacrylate and ethylene oxide adducts or propylene oxide adducts of these phenols; Acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether, and triglycidyl isocyanurate; Polyfunctional or monofunctional polyurethane acrylate which is an isocyanate modified product of the hydroxyalkyl acrylate; And melamine acrylate, and each (meth) acrylate corresponding to the acrylate, or 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacryl Hydroxyalkyl acrylates such as rate; Mono or diacrylates of glycols such as ethylene glycol, methoxy tetraethylene glycol, polyethylene glycol and propylene glycol; Acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide and N, N-dimethylaminopropylacrylamide; Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; Polyhydric acrylates such as polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or ethylene oxide adducts or propylene oxide adducts thereof; Acrylates such as phenoxyacrylate, bisphenol A diacrylate and ethylene oxide adducts or propylene oxide adducts of these phenols; Acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; Polyfunctional or monofunctional polyurethane acrylate which is an isocyanate modified product of the hydroxyalkyl acrylate; And melamine acrylate or each (meth) acrylate corresponding to the said acrylate, etc. are mentioned, These can be used individually or in combination of 2 or more types. Among these, compounds having two or more radically polymerizable unsaturated groups in one molecule, for example, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, and the like are preferable because of excellent photocurability.

In addition, this compound may be called a polymerizable monomer below.

The compounding quantity of such a polymerizable monomer (D) becomes like this. Preferably it is 5-100 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (A), More preferably, it is the ratio of 10-70 mass parts. When the said compounding quantity is too small, since photocurability falls and the pattern formation by alkali image development after active energy ray irradiation becomes difficult, it is unpreferable. On the other hand, when too much, since the solubility to aqueous alkali solution falls or a coating film becomes weak, it is unpreferable.

(E-1) As a specific example of the oxime system photoinitiator represented by the said Formula (1), a 1, 2- octanedione-1- [4- (phenylthio) -2- (O- benzoyl oxime)], ethanone -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), and 2- (acetyloxyiminomethyl represented by the following formula (7): ) Thioxanthene-9-one is mentioned.

Among these, 2- (acetyloxyiminomethyl) thioxanthene-9-one which is a compound represented by the said Formula (7) is especially preferable. Commercially available products include CGI-325 manufactured by Ciba Specialty Chemicals.

As a compounding quantity of such a photoinitiator (E-1), when using (C-1) black pigment as (C), it is 0.01-20 mass with respect to 100 mass parts of said carboxyl group-containing resin (A) preferably. Part, more preferably 0.01 to 5 parts by mass. Moreover, when using (C-2) silver powder as (C), the ratio of 0.1-1.0 mass% of the whole composition is preferable. In this case, the compounding quantity of the oxime system photoinitiator (E-1) based on 100 mass parts of said carboxyl group-containing resin (A) is a glass frit, silver powder, the compound which has one or more radically polymerizable unsaturated groups in 1 molecule, and organic Although a preferable range changes with the compounding quantity of a solvent, it is a ratio of 0.01-20 mass parts, Preferably it is 0.05-10 mass parts, More preferably, it is 0.5-5.0 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (A). . When the compounding quantity of an oxime system photoinitiator (E-1) is too large with respect to 100 mass parts of said carboxyl group-containing resin (A), since sufficient photocurability is not obtained, it is unpreferable. On the other hand, when too small, thick film sclerosis | hardenability falls and it leads to the cost increase of a product, and it is not preferable.

It is preferable to mix | blend the phosphine oxide type photoinitiator (E-2) containing the structure represented by the said Formula (4) in order for the alkali developing paste composition of this invention to further high sensitivity.

Examples of such phosphine oxide-based photopolymerization initiator (E-2) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and bis (2,6 -Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, etc. are mentioned.

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

In addition, it is highly sensitive that the compounding quantity of the oxime type photoinitiator (E-1) represented by the said Formula (1) is at least equivalent or less than the compounding quantity of the phosphine oxide type photoinitiator (E-2) represented by the said Formula (4). It is preferable in order to obtain thick film sclerosis | hardenability.

The alkali developing paste composition of this invention can use together a well-known conventional photoinitiator further as needed. Specifically, benzoin and benzoin alkyl ether, such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, etc. Acetophenones; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone- Aminoacetophenones such as 1; Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone and 1-chloroanthraquinone; Thioxanthones, such as 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2-chloro thioxanthone, and 2, 4- diisopropyl thioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone; Or xanthones; (2,6-dimethoxybenzoyl) -2,4,4-pentylphosphineoxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine jade Phosphine oxides, such as a seed and ethyl-2,4,6-trimethylbenzoylphenyl phosphinate, etc. are mentioned. In particular, Thioxanthone type photoinitiators, such as 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2-chloro thioxanthone, and 2, 4- diisopropyl thioxanthone, or bis | It is preferable to use together a phosphine oxide type photoinitiator, such as (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, from the point of deep-curing property.

The compounding quantity of such thioxanthone type photoinitiator or phosphine oxide type photoinitiator becomes like this. Preferably it is 30 mass parts or less, More preferably, it is the ratio of 20 mass parts or less with respect to 100 mass parts of said carboxyl group-containing resin (A). . When the compounding quantity of these thioxanthone type photoinitiators is too large, since thick film sclerosis | hardenability will fall and it will lead to the cost increase of a product, it is unpreferable.

(F) sulfur compound represented by the formula (2)

This sulfur compound is mix | blended in order to improve the sensitivity regarding the laser beam of a composition. This inventor guesses the reason as follows. In the light irradiation site, as the radical polymerization reaction proceeds, diffusion of the polymerizable monomer (D) is unlikely to occur, and a decrease in the polymerization rate or the reaction rate may occur and an unreacted polymerizable monomer (D) may remain. However, by adding the sulfur compound (F) which acts as a chain transfer agent, it is thought that the polymerization reaction proceeds efficiently, the reaction rate is increased, and as a result, high sensitivity can be achieved.

(G) boric acid

Moreover, it is preferable that boric acid (G) is added to the alkali developing type paste composition of this invention in order to improve storage stability.

As such boric acid (G), an average particle diameter (D ₅₀ ) micronized 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 divided in this way tends to be hygroscopic and re-agglomerate, so it is preferable to use it immediately after grinding. 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). When the compounding ratio of boric acid is too small with respect to 100 mass parts of said glass frits (B), since there is no improvement effect of storage stability, it is not preferable.

In addition, when mix | blending boric acid (G) in this way, it is necessary to use the hydrophobic solvent whose solubility with respect to 100 g of water of 25 degreeC is 20 g or less. When an organic solvent having high solubility in water is used, water dissolved in the organic solvent is not preferable because ionization of the metal contained in the glass frit causes gelation.

(H) phosphorus compounds

Moreover, in order to improve the storage stability of the alkali developing type paste composition of this invention, it is preferable to mix | blend the phosphorus compound (H) represented by the said Formula (5) or (6).

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 phosphite, dipropyl phosphite, diphenyl phosphite, isopropyl phosphite, diisopropyl phosphite, n-butyl phosphite 2-ethylhexyl hydroxyethylenediphosphonic acid, adenosine triphosphate, adenosine phosphoric acid, mono (2-methacryloyloxyethyl) acid phosphate, mono (2-acryloyloxyethyl) acid phosphate, di (2-metha) Chloroyloxyethyl) phosphate, di (2-acryloyloxyethyl) phosphate, ethyl diethyl phosphonoacetate, ethyl phosphate, butyl phosphate, butyl pyrophosphate, butoxyethyl phosphate Byte, a 2-ethylhexyl phosphate acids, oleic monoxide phosphate, tetra-phosphate co-acids, diethylene glycol acid phosphate, (2-hydroxyethyl) and the like methacrylate acid phosphate. These phosphorus compounds can be used individually or in combination of 2 or more types.

The compounding quantity of these phosphorus compounds (H) is 10 mass parts or less with respect to 100 mass parts of said glass frits (B), More preferably, it is 0.1-5 mass parts. When the compounding quantity of the phosphorus compound (H) is too large with respect to 100 mass parts of said glass frits (B), since plasticity falls, it is not preferable.

(Other formulations)

The alkali developing paste composition of this invention can use an organic solvent for the synthesis | combination of the said carboxyl group-containing resin (A), adjustment of a composition, or viscosity adjustment for apply | coating to a board | substrate or a carrier film. Specifically, Ketones, such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; Glycol ethers such as cellosolve, methyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether ; Acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol, propylene glycol and terpineol; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents, such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha, are mentioned, These can be used individually or in combination of 2 or more types.

The alkali-developing paste composition of the present invention may further contain, if necessary, known conventional thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol and phenothiazine, finely divided silica and organic bentonite. Known conventional thickeners such as montmorillonite, antifoaming agents and / or leveling agents such as silicone-based, fluorine-based, and polymer-based, and silane coupling agents such as imidazole-based, thiazole-based, and triazole-based additives. .

(Use of composition)

As described above, the alkali-developing paste composition of the present invention is adjusted to a viscosity suitable for a coating method with the organic solvent, for example, by a flow coating method, a roll coating method, a bar coater method, a screen printing method, It is apply | coated by methods, such as a curtain coating method, and it can dry for about 5 to 40 minutes at about 60-120 degreeC, for example, and can form a tack-free coating film. Or the tack free coating film can be formed by apply | coating the said composition on a carrier film, drying, and laminating | stacking the thing wound as a film on a board | substrate.

Moreover, it is preferable from the viewpoint of pattern formation that the absorbance per film thickness of 1 micrometer of a dry coating film in this way is 0.1-0.8.

Thereafter, the photomask having a pattern formed by a contact type (or non-contact method) is selectively exposed with an active energy ray, and the unexposed portion is diluted with an aqueous alkali solution (for example, 0.3 to 3% aqueous sodium carbonate solution). It develops and a pattern is formed.

As an exposure machine used for the said active energy ray irradiation, a direct drawing apparatus (for example, the laser direct imaging apparatus which draws an image with a laser directly by CAD data from a computer) can be used. As an active energy source, a laser diode, a gas laser, a solid laser, etc. which emit the laser beam in the range whose maximum wavelength is 350 nm-420 nm are mentioned, Especially a laser diode is preferable.

As the direct drawing apparatus, for example, Nippon Olbotec Co., Pentax Co., Hitachi Beer Mechanics Co., Ball Semiconductor Co., Ltd. product or the like can be used, and any device may be used.

Moreover, in addition to the said direct drawing apparatus, you may use the conventional exposure machine. As the light source, halogen lamps, high pressure mercury lamps, laser lights, metal halide lamps, black lamps, electrodeless lamps and the like are used.

In addition, a spraying method, an immersion method, etc. are used for the said image development. As a developing solution, aqueous solution of metal alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium silicate, and aqueous solution of amines, such as monoethanolamine, diethanolamine, triethanolamine, and tetramethylammonium hydrooxide, especially about 1.5 mass% Although the diluted alkali aqueous solution of the following density | concentration is used preferably, the carboxyl group of the carboxyl group-containing resin (A) in a composition may be saponified, and the unhardened part (unexposed part) may be removed, and is not limited to the above-mentioned developing solution. In addition, it is preferable to perform washing with water or neutralizing the acid to remove unnecessary developer after development.

The substrate patterned by the above development may be baked at about 400 to 600 ° C. in air or under a nitrogen atmosphere to form a desired pattern.

<Example>

Although an Example and a comparative example are given to the following and this invention is demonstrated concretely, this invention is not limited to the following Example.

Synthesis Example  1: Synthesis of Carboxyl Group-Containing Resin

Methyl methacrylate and methacrylic acid were injected into a flask equipped with a thermometer, a stirrer, a dropping lot, and a reflux condenser at a molar ratio of 0.87: 0.13, dipropylene glycol monomethyl ether as a solvent, and azobisisobutyronitrile as a catalyst. Was added, and the mixture was 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 was made by Shimadzu Seisakusho Pump LC-6AD, Showa Denko Co., Ltd. Shodex (trademark) KF-804, KF-803, KF-802 It was measured by high performance liquid chromatography of three connected. Hereinafter, this carboxyl group-containing resin solution is called A-1 varnish.

Synthesis Example  2: synthesis of carboxyl group-containing photosensitive resin

The injection ratio of methyl methacrylate and methacrylic acid to a flask equipped with a thermometer, a stirrer, a dropping lot, and a reflux condenser was set to 0.76: 0.24 in molar ratio, dipropylene glycol monomethyl ether as a solvent, and azobisisobutyine as a catalyst. A ronitrile was added and stirred for 6 hours at 80 ° C. under a nitrogen atmosphere to obtain a carboxyl group-containing resin solution. This carboxyl group-containing resin solution was cooled, and glycidyl methacrylate was used at 95 to 105 DEG C for 16 hours using methylhydroquinone as a polymerization inhibitor and tetrabutylphosphonium bromide as a catalyst. The addition reaction was carried out at an addition molar ratio of 0.12 mol relative to, and 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 called A-2 varnish.

Example  1 to 18 and Comparative example  1 to 2

The compounding components shown in following Table 1 and Table 2 using A-1 varnish and A-2 varnish obtained in the said Synthesis Examples 1 and 2 were kneaded with a triaxial roll mill to obtain an alkali developing paste composition.

Using the alkali-developing black paste compositions of Examples 1 to 9 and Comparative Example 1 of Table 1 above, the coating was applied to the entire surface using a 300 mesh polyester screen on a glass substrate. Subsequently, it dried for 20 minutes at 90 degreeC using the hot-air circulation type drying furnace, and formed the film of favorable touch drying property. Subsequently, using a stripe-shaped CAD data having a line width of 100 μm and a space width of 150 μm, the composition was a laser direct imaging exposure apparatus (DI-μ10 manufactured by Pentax) having a blue violet laser having a center wavelength of 405 nm as a light source. The exposure was performed so that the accumulated light amount of the phase became 40 mJ / cm 2. Then, using a 0.4 wt.% Na ₂ CO ₃ aqueous solution of a liquid temperature of 30 ℃ was washed subjected to developing for 20 seconds. Finally, it was calcined in air using an electric furnace.

In addition, baking was heated at a temperature increase rate of 5 ° C / min from room temperature to 590 ° C, held at 590 ° C for 10 minutes, and then cooled to room temperature.

The evaluation results of the various characteristics of each substrate thus obtained are shown in Table 3 below.

In addition, the evaluation method in Table 3 is as follows.

(1) measurement of absorbance

The absorbance of the evaluation board | substrate which formed the coating film of 5 micrometers of dry film thickness, and 10 micrometers in soda-lime glass was measured using the ultraviolet visible spectrophotometer. The absorbance per 1 micrometer in thickness in 405 nm was computed from the obtained data.

(2) evaluation of laser photosensitivity

The line of L / S = 100/150 μm was exposed at a cumulative light amount of 50 mJ / cm 2, and developed for 20 seconds using an aqueous solution of 0.4 wt% Na ₂ CO ₃ at a liquid temperature of 30 ° C. Evaluated. Evaluation criteria are as follows.

(Circle): A defect is not seen at all.

(Triangle | delta): A some defect is seen.

X: A line cannot be formed.

(3) Calculation of minimum exposure dose

Exposure was performed by changing the accumulated light amount, and the minimum exposure amount capable of forming a line of L / S = 100/150 µm without a defect was measured. In addition, since the exposure time with a laser became long and it was not practical, the comparative example did not perform subsequent tests.

(4) Line shape after pattern formation

When exposing at the said minimum exposure amount, the pattern after the image development in the alkali paste type black paste composition was observed under the microscope, and the evaluation evaluated the presence or absence of the irregular fluctuation | variation in a line | wire or a twist. Evaluation criteria are as follows.

(Circle): There are no irregular fluctuations or twisting.

(Triangle | delta): There exist some irregular fluctuations and a torsion.

X: There are irregular fluctuations and torsion.

(5) line shape after firing

The line shape after baking observed the pattern which terminated to baking by the microscope, and evaluated the presence or absence of the irregular fluctuation | variation in a line, or torsion. Evaluation criteria are as follows.

(Circle): There are no irregular fluctuations or twisting.

(Triangle | delta): There exist some irregular fluctuations and a torsion.

X: There are irregular fluctuations and torsion.

(6) adhesion

Adhesiveness was performed with the cellophane adhesive tape, and it evaluated with or without pattern peeling. Evaluation criteria are as follows.

(Circle): There is no peeling of a pattern.

(Triangle | delta): There exists a peeling of a pattern slightly.

X: There are many peelings of a pattern.

As is apparent from the results shown in Table 3, it can be seen that the alkali-developed black paste composition of the present invention has sufficient sensitivity to the active energy ray, so that high-precision fine pattern formation is possible. Moreover, there was no irregular variation in the line shape after baking, and adhesiveness with the base material was also excellent.

Moreover, the blackness after baking was also satisfactory, and was excellent also in storage stability.

Subsequently, pattern formation in lamp type exposure was also performed. Using the alkali paste type black paste composition of Examples 1-9 and Comparative Example 1, it was applied to the entire surface on a glass substrate using a 300 mesh polyester screen. Subsequently, it dried for 20 minutes at 90 degreeC using the hot-air circulation type drying furnace, and formed the film of favorable touch drying property. Subsequently, the cumulative amount of light on the paste was used with an exposure apparatus (MAT-5301 manufactured by Hakuto Co., Ltd.) having an ultra-high pressure mercury lamp as a light source, using a glass dry plate having a stripe negative pattern having a line width of 100 μm and a space width of 150 μm as a photomask. It exposed so that it might become 50 mJ / cm <2>. Then, using a 0.4 mass% Na ₂ CO ₃ aqueous solution of a liquid temperature of 30 ℃ was washed subjected to developing for 20 seconds. Finally, it was calcined in air using an electric furnace.

In addition, baking was heated at a temperature increase rate of 5 ° C / min from room temperature to 590 ° C, held at 590 ° C for 10 minutes, and then cooled to room temperature.

The evaluation results of the various characteristics of each substrate thus obtained are shown in Table 4 below. In addition, the evaluation method of Table 4 is as follows.

(1) evaluation of photosensitivity

The line of L / S = 100/150 μm was exposed at a cumulative light amount of 50 mJ / cm 2, and development was performed for 20 seconds using a 0.4 wt% Na ₂ CO ₃ aqueous solution having a liquid temperature of 30 ° C., and an optical microscope was used to determine whether lines were formed. Evaluated. Evaluation criteria are as follows.

(Circle): A defect is not seen at all.

(Triangle | delta): A some defect is seen.

X: A line cannot be formed.

(2) Calculation of minimum exposure dose

Exposure was performed by changing the accumulated light amount, and the minimum exposure amount capable of forming a line of L / S = 100/150 µm without a defect was measured.

(3) line shape after pattern formation

When exposing at the said minimum exposure amount, the pattern after the image development in the alkali paste type black paste composition was observed under the microscope, and the evaluation evaluated the presence or absence of the irregular fluctuation | variation in a line | wire or a twist. Evaluation criteria are as follows.

(Circle): There are no irregular fluctuations or twisting.

(Triangle | delta): There exist some irregular fluctuations and a torsion.

X: There are irregular fluctuations and torsion.

(4) line shape after firing

The line shape after baking observed the pattern completed until baking with the microscope, and evaluated the presence or absence of the irregular fluctuation | variation in a line, or torsion. Evaluation criteria are as follows.

(Circle): There are no irregular fluctuations or twisting.

(Triangle | delta): There exist some irregular fluctuations and a torsion.

X: There are irregular fluctuations and torsion.

(5) adhesion

Adhesiveness was performed with the cellophane adhesive tape, and it evaluated with or without pattern peeling. Evaluation criteria are as follows.

(Circle): There is no peeling of a pattern.

(Triangle | delta): There exists a peeling of a pattern slightly.

X: Peeling of a pattern is frequent.

As is apparent from the results shown in Table 4, it was found that the alkali paste-type black paste composition of the present invention had sufficient sensitivity even when an ultrahigh pressure mercury lamp was used as a light source to form a high-precision fine pattern.

The alkali paste-type silver paste composition of Examples 10-18 and Comparative Example 2 was used, and it apply | coated to the whole surface using the 300-mesh polyester screen on the glass substrate. Subsequently, it dried for 20 minutes at 90 degreeC using the hot-air circulation type drying furnace, and formed the film of favorable touch drying property. Subsequently, using a stripe-shaped CAD data having a line width of 50 µm and a space width of 200 µm, the composition was a laser direct imaging exposure apparatus (DI-μ10 manufactured by Pentax) having a blue-violet laser having a center wavelength of 405 nm as a light source. The exposure was performed so that the accumulated light amount of the phase became 40 mJ / cm 2. Then, using a 0.4 wt.% Na ₂ CO ₃ aqueous solution of a liquid temperature of 30 ℃ was washed subjected to developing for 20 seconds. Finally, it was calcined in air using an electric furnace.

In addition, baking was heated at a temperature increase rate of 5 ° C / min from room temperature to 590 ° C, held at 590 ° C for 10 minutes, and then cooled to room temperature.

The evaluation results of the various characteristics of each substrate thus obtained are shown in Table 5 below.

In addition, the evaluation method in Table 5 is as follows.

(1) measurement of absorbance

The absorbance of the evaluation board | substrate which formed the coating film of 5 micrometers of dry film thickness, and 10 micrometers in soda-lime glass was measured using the ultraviolet visible spectrophotometer. The absorbance per 1 micrometer in thickness in 405 nm was computed from the obtained data.

(2) evaluation of laser photosensitivity

A line of L / S = 50/200 μm was exposed at a cumulative light amount of 50 mJ / cm 2, and developed for 20 seconds using an aqueous solution of 0.4 wt% Na ₂ CO ₃ at a liquid temperature of 30 ° C. Evaluated. Evaluation criteria are as follows.

(Circle): A defect is not seen at all.

(Triangle | delta): A some defect is seen.

X: A line cannot be formed.

(3) Calculation of minimum exposure dose

Exposure was performed by changing the accumulated light amount, and the minimum exposure amount capable of forming a line of L / S = 50/200 µm without a defect was measured. In addition, since the exposure time with a laser became long and it was not practical, the comparative example did not perform subsequent tests.

(4) Line shape after pattern formation

When exposing at the said minimum exposure amount, the pattern after image development in the alkali paste type silver paste composition was observed under the microscope, and it evaluated the presence or absence of the irregular fluctuation | variation in a line, a distortion, etc. in a line. Evaluation criteria are as follows.

(Circle): There are no irregular fluctuations or twisting.

(Triangle | delta): There exist some irregular fluctuations and a torsion.

X: There are irregular fluctuations and torsion.

(5) line shape after firing

The line shape after baking observed the pattern which terminated to baking by the microscope, and evaluated the presence or absence of the irregular fluctuation | variation in a line, or torsion. Evaluation criteria are as follows.

(Circle): There are no irregular fluctuations or twisting.

(Triangle | delta): There exist some irregular fluctuations and a torsion.

X: There are irregular fluctuations and torsion.

(6) adhesion

Adhesiveness was performed with the cellophane adhesive tape, and it evaluated with or without pattern peeling. Evaluation criteria are as follows.

(Circle): There is no peeling of a pattern.

(Triangle | delta): There exists a peeling of a pattern slightly.

X: There are many peelings of a pattern.

(7) Measurement of specific resistance value

The test board | substrate was manufactured like the evaluation of said (line shape after baking) except having exposed using CAD data of a pattern dimension of 0.4 cm x 10 cm. The resistivity value of the baked film was measured about the test board | substrate thus obtained using the Milio Ohm tester, and the film thickness of the baked film was measured using the surf coater, and the specific resistance value of the baked film was computed.

As is clear from the results shown in Table 5, it is understood that the alkali paste-type silver paste composition of the present invention has sufficient sensitivity to laser light, so that high-precision fine pattern formation is possible. Moreover, there was no irregular variation in the line shape after baking, the specific resistance value was sufficient as an electrode material, adhesiveness with a base material was also favorable, and it was excellent in storage stability.

Subsequently, pattern formation in lamp type exposure was also performed. The alkali development silver paste compositions of Examples 10 to 18 and Comparative Example 2 were used, and were applied to the entire surface on a glass substrate using a 300 mesh polyester screen. Subsequently, it dried for 20 minutes at 90 degreeC using the hot-air circulation type drying furnace, and formed the film of favorable touch drying property. Subsequently, a cumulative amount of light in a paste was formed using an exposure apparatus (MAT-5301 manufactured by Hakuto Co., Ltd.) having an ultrahigh pressure mercury lamp as a light source, using a glass dry plate having a stripe negative pattern having a line width of 50 µm and a space width of 200 µm as a photomask. It exposed so that it might become 40 mJ / cm <2>. Then, using a 0.4 mass% Na ₂ CO ₃ aqueous solution of a liquid temperature of 30 ℃ was washed subjected to developing for 20 seconds. Finally, it was calcined in air using an electric furnace.

In addition, baking was heated at a temperature increase rate of 5 ° C / min from room temperature to 590 ° C, held at 590 ° C for 10 minutes, and then cooled to room temperature.

The evaluation results of the various characteristics of each substrate thus obtained are shown in Table 6 below. In addition, the evaluation method of Table 6 is as follows.

(1) evaluation of photosensitivity

A line of L / S = 50/200 μm was exposed at a cumulative light amount of 50 mJ / cm 2, and developed for 20 seconds using an aqueous solution of 0.4 wt% Na ₂ CO ₃ at a liquid temperature of 30 ° C. Evaluated. Evaluation criteria are as follows.

(Circle): A defect is not seen at all.

(Triangle | delta): A some defect is seen.

X: A line cannot be formed.

(2) Calculation of minimum exposure dose

Exposure was performed by changing the accumulated light amount, and the minimum exposure amount capable of forming a line of L / S = 50/200 µm without a defect was measured.

(3) line shape after pattern formation

When exposing at the said minimum exposure amount, the pattern after image development in the alkali paste type silver paste composition was observed under the microscope, and it evaluated the presence or absence of the irregular fluctuation | variation in a line, a distortion, etc. in a line. Evaluation criteria are as follows.

(Circle): There are no irregular fluctuations or twisting.

(Triangle | delta): There exist some irregular fluctuations and a torsion.

X: There are irregular fluctuations and torsion.

(4) line shape after firing

The line shape after baking observed the pattern completed until baking with the microscope, and evaluated the presence or absence of the irregular fluctuation | variation in a line, or torsion. Evaluation criteria are as follows.

(Circle): There are no irregular fluctuations or twisting.

(Triangle | delta): There exist some irregular fluctuations and a torsion.

X: There are irregular fluctuations and torsion.

(5) adhesion

Adhesiveness was performed with the cellophane adhesive tape, and it evaluated with or without pattern peeling. Evaluation criteria are as follows.

(Circle): There is no peeling of a pattern.

(Triangle | delta): There exists a peeling of a pattern slightly.

X: Peeling of a pattern is frequent.

As apparent from the results shown in Table 6, it was found that the alkali-developed silver paste composition of the present invention had sufficient sensitivity even when an ultra-high pressure mercury lamp was used as a light source, thereby forming a high-precision fine pattern.

Example  19 to 26 and Comparative example  3

The compounding components shown in Table 7 below using A-1 varnish and A-2 varnish obtained in the above synthesis example were kneaded with three roll mills to obtain an alkali developing black silver paste composition.

Evaluation of the alkali developing type black silver paste composition which contains both a black pigment and silver powder as an inorganic component was also performed. Using the black silver paste composition of the said Examples 19-26 and the comparative example 3, it applied to the whole surface using the 300-mesh polyester screen on the glass substrate. Subsequently, it dried for 20 minutes at 90 degreeC using the hot-air circulation type drying furnace, and formed the film of favorable touch drying property. Subsequently, a cumulative amount of light in a paste was formed using an exposure apparatus (MAT-5301 manufactured by Hakuto Co., Ltd.) having an ultrahigh pressure mercury lamp as a light source, using a glass dry plate having a stripe negative pattern having a line width of 50 µm and a space width of 200 µm as a photomask. It exposed so that it might become 40 mJ / cm <2>. Then, using a 0.4 mass% Na ₂ CO ₃ aqueous solution of a liquid temperature of 30 ℃ was washed subjected to developing for 20 seconds. Finally, it was calcined in air using an electric furnace.

In addition, baking was heated at a temperature increase rate of 5 ° C / min from room temperature to 590 ° C, held at 590 ° C for 10 minutes, and then cooled to room temperature.

The evaluation results of the various characteristics of each substrate thus obtained are shown in Table 8 below. In addition, the evaluation method of Table 8 is as follows.

(1) measurement of absorbance

The absorbance of the evaluation board | substrate which formed the coating film of 5 micrometers of dry film thickness, and 10 micrometers in soda-lime glass was measured using the ultraviolet visible spectrophotometer. From the obtained data, the absorbance per 1 micrometer in thickness at 405 nm was computed.

(2) evaluation of photosensitivity

A line of L / S = 50/200 μm was exposed at a cumulative light amount of 50 mJ / cm 2, and developed for 20 seconds using an aqueous solution of 0.4 wt% Na ₂ CO ₃ at a liquid temperature of 30 ° C. Evaluated. Evaluation criteria are as follows.

(Circle): A defect is not seen at all.

(Triangle | delta): A some defect is seen.

X: Lines cannot be formed.

(3) Calculation of minimum exposure dose

Exposure was performed by changing the accumulated light amount, and the minimum exposure amount capable of forming a line of L / S = 50/200 µm without a defect was measured.

(4) Line shape after pattern formation

When exposing at the said minimum exposure amount, the pattern after image development in the alkali silver type black silver paste composition was observed under the microscope, and it evaluated with the presence or absence of the irregular fluctuation | variation in a line | wire, or a torsion. Evaluation criteria are as follows.

(Circle): There are no irregular fluctuations or twisting.

(Triangle | delta): There exist some irregular fluctuations and a torsion.

X: There are irregular fluctuations and torsion.

(5) line shape after firing

The line shape after baking observed the pattern completed until baking with the microscope, and evaluated the presence or absence of the irregular fluctuation | variation in a line, or torsion. Evaluation criteria are as follows.

(Circle): There are no irregular fluctuations or twisting.

(Triangle | delta): There exist some irregular fluctuations and a torsion.

X: There are irregular fluctuations and torsion.

(6) adhesion

Adhesiveness was performed with the cellophane adhesive tape, and it evaluated with or without pattern peeling. Evaluation criteria are as follows.

(Circle): There is no peeling of a pattern.

(Triangle | delta): There exists a peeling of a pattern slightly.

X: Peeling of a pattern is frequent.

(7) Measurement of specific resistance value

The test board | substrate was manufactured like the evaluation of said (line shape after baking) except having exposed using the photomask in which the pattern of pattern size 0.4 cm x 10 cm was formed. About the test board | substrate obtained in this way, the resistance value of the baking film was measured using the Milio Ohm tester, and the film thickness of the baking film was measured using the surf coater, and the specific resistance value of the baking film was computed.

As apparent from the results shown in Table 8, it was found that the alkali developing black silver paste composition of the present invention had sufficient sensitivity to form a high-precision fine pattern.

The alkali-developing paste composition of the present invention has a sufficient sensitivity to an active energy ray by blending the sulfur compound represented by the formula (2), and can form a high precision pattern.

Moreover, since the said paste composition has sufficient sensitivity with respect to an active energy ray, exposure can be performed in a short time, and the time required for exposure is shortened, and it becomes possible to raise the manufacturing efficiency of a pattern.

Moreover, since it shows the outstanding photocurability with respect to the active energy ray whose maximum wavelength is 350 nm-420 nm, a laser direct imaging apparatus can be used as an exposure apparatus, and it becomes possible to form a highly reliable pattern.

Claims (17)

(A) carboxyl group-containing resin, (B) glass frit, (C) inorganic powder, (D) compound which has at least 1 radically polymerizable unsaturated group in 1 molecule, (E-1) oxime system represented by following General formula (1) An alkali developing paste composition comprising a polymerization initiator and (F) a sulfur compound represented by the following general formula (2). <Formula 1>

(In formula, R <^1> represents a hydrogen atom, a C1-C6 alkyl group, or a phenyl group, R <^2> represents a hydrogen atom, a C1-C6 alkyl group.) <Formula 2>

(Wherein 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 may combine with each other to include a hetero atom selected from oxygen, sulfur and nitrogen atoms) Represents a group of nonmetallic atoms required to form a 5- to 7-membered ring) The alkali developing type paste composition of Claim 1 whose said oxime system photoinitiator (E-1) is an oxime system photoinitiator represented by following formula (3). <Formula 3>

(Wherein one or two R ⁵ is represented by the following formula (1), provided that when two R ⁵ is represented by the formula (1), R ⁵ is different from each other), and the remaining R ⁵ is a hydrogen atom , Methyl, phenyl or halogen atom (where each R ⁵ is different) <Formula 1>

(In formula, R <^1> represents a hydrogen atom, a C1-C6 alkyl group, or a phenyl group, R <^2> represents a hydrogen atom, a C1-C6 alkyl group.) The alkali-developing paste composition according to claim 1 or 2, wherein the carboxyl group-containing resin (A) is (A-1) a carboxyl group-containing resin further having at least one radical polymerizable unsaturated group. The alkali-developing paste composition according to claim 1 or 2, further comprising (E-2) a phosphine oxide-based photoinitiator represented by the following general formula (4). <Formula 4>

(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 an aryl group substituted with a halogen atom, an alkyl group or an alkoxy group, Or any one represents a carbonyl group having 1 to 20 carbon atoms) The compounding quantity of the oxime type photoinitiator (E-1) represented by the said Formula (1) is less than the compounding quantity of the phosphine oxide type photoinitiator (E-2) represented by the said Formula (4). An alkali developing paste composition. The alkali-developing paste composition according to claim 1 or 2, further comprising (G) boric acid. The alkali-developing paste composition according to claim 1 or 2, further comprising (H) a phosphorus compound represented by the following general formula (5) or (6). <Formula 5>

<Formula 6>

The alkali developing paste composition according to any one of claims 1 to 7, wherein the absorbance is 0.1 to 0.8 per film thickness of the coated film coated with the composition. The alkali-developing paste composition according to claim 1 or 2, wherein the inorganic powder (C) is a black pigment (C-1), silver powder (C-2), or both. It is a formation method of the pattern using the composition of any one of Claims 1-9, (1) a step of pattern exposing with an active energy ray, (2) process of forming pattern selectively by developing with dilute aqueous alkali solution, (3) step of baking at 400 to 600 ° C Forming method of a pattern comprising a. The pattern forming method according to claim 10, wherein the active energy ray is a laser oscillation light source or a lamp light source. The pattern obtained by the formation method of the pattern of Claim 10 or 11. The pattern according to claim 12, wherein the pattern is a conductive pattern. The pattern of claim 12 or 13, wherein the pattern comprises a black matrix pattern. The plasma display panel containing the pattern formed using the alkali developing type paste composition in any one of Claims 1-9. The plasma display panel containing the pattern of any one of Claims 12-14. The alkali developing type paste composition of Claim 1 or 2 whose compounding quantity of the oxime system photoinitiator (E-1) represented by the said General formula (1) is 0.1-1.0 mass% of the total amount of a composition.