JP2009042732A - Photosensitive composition and pattern made of its baked product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alkali developable photosensitive composition capable of effectively suppressing the occurrence of defects such as a pinhole and a chip in a line during patterning, and to provide a pattern made of a baked product of the composition and free of defects such as a pinhole and a chip in a line. <P>SOLUTION: The alkali developable photosensitive composition has (A) a carboxylic resin, (B) an inorganic component, (C) a compound having a radical polymerizable unsaturated group, and (D-1) a liquid phosphine oxide-based photopolymerization initiator. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photosensitive composition suitable for forming a black matrix pattern, a conductive pattern, a partition pattern, etc. in various thin displays such as a plasma display panel, a field emission display, and a liquid crystal display device, and a pattern comprising a fired product thereof. It is about.

  In thin displays, various patterns such as a black matrix pattern, a conductive pattern (electrode circuit), and a partition pattern are used. As the formation method, for example, a resist for pattern formation is applied 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 a circuit or an electrode pattern is drawn, and then an exposed portion. The resist layer corresponding to the circuit and electrode pattern is formed by developing with an alkaline aqueous solution utilizing the difference in solubility in the developer in the unexposed area and the unexposed area, and a pattern closely adhered to the glass substrate is formed by baking. It was.

  Recently, 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. Various photosensitive paste compositions suitable for the patterning method have been developed because it has many advantages such as eliminating the need for foreign matter adhesion, dirt, and scratch management (see, for example, Patent Documents 1 to 3). reference).

However, in any patterning method, it is difficult to eliminate defects such as pinholes, line defects, line short circuits, line open defects, etc. that occur during patterning. The development of a photosensitive composition that can provide the above has been awaited.
JP 2002-351071 A (Claims) JP 2002-351072 A (Claims) JP 2004-45596 A (Claims)

  The present invention was developed in view of the above problems, and provides an alkali development type photosensitive composition capable of effectively suppressing the occurrence of defects such as pinholes and line defects generated during patterning. It is another object of the present invention to provide a pattern free from defects such as pinholes and line defects made of a fired product of the composition.

  In order to achieve the above object, even when the appearance is uniform as a paste due to cooling during storage, crystal precipitation of the photopolymerization initiator, which is an additive, occurs, and this causes defects in the coating film. It was found that

  That is, in the first embodiment, the present invention provides (A) a carboxyl group-containing resin, (B) an inorganic component, (C) a compound having a radical polymerizable unsaturated group, and (D-1) a liquid phosphine oxide system. An alkali development type photosensitive composition containing a photopolymerization initiator.

  According to one aspect of the present invention, the inorganic component (B) is selected from (B-1) a colorant exhibiting black color, (B-2) silver powder, and (B-3) glass powder.

Moreover, according to the other aspect of this invention, a liquid phosphine oxide type photoinitiator (D-1) contains the structure represented by the following general formula (I).

In the formula, R ¹ is a linear or branched alkyl group having 1 to 12 carbon atoms, and R ² is substituted with a cyclohexyl group, a cyclopentyl group, an aryl group, a halogen atom, an alkyl group or an alkoxy group. An aryl group or a C1-C20 carbonyl group is represented.

  In another embodiment of the present invention, the blending ratio of the oxime photopolymerization initiator (D-2) is less than the blending ratio of the phosphine oxide photopolymerization initiator (D-1).

  In another aspect of the present invention, the absorbance per 1 μm film thickness of a coating film obtained by diluting the photosensitive composition of the present invention with an organic solvent and coating and drying is 0.01 to 0.8.

  This invention is a pattern which consists of a baked product of the said photosensitive composition in 2nd form.

  Since the photosensitive composition of the present invention using the liquid phosphine oxide photopolymerization initiator (D-1) as a photopolymerization initiator does not cause crystal precipitation of the photopolymerization initiator due to low-temperature storage, There are no foreign substances in the paste after refrigerated storage that can induce coating film defects. Therefore, according to the present invention, it is possible to provide various pattern fired products having no defects such as pinholes and chipping of lines.

  The photosensitive composition of the present invention comprises (A) a carboxyl group-containing resin, (B) an inorganic component, (C) a compound having a radical polymerizable unsaturated group, and (D-1) a liquid phosphine oxide photopolymerization initiation. In a preferred embodiment, the liquid phosphine oxide photopolymerization initiator (D-1) includes a structure represented by the above general formula (I). .

Hereinafter, each structural component of the photosensitive composition of this invention is demonstrated in detail.
As the carboxyl group-containing resin (A) contained in the photosensitive composition of the present invention, a resin compound containing a carboxyl group in the molecule can be used. Furthermore, a carboxyl group-containing photosensitive resin (A ′) having a radically polymerizable unsaturated double bond in the molecule is more preferable from the viewpoints of photocurability and development resistance.
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 saturated or unsaturated polybasic acid anhydride with a hydroxyl group-containing polymer such as a polyvinyl alcohol derivative, the resulting carboxylic acid is reacted with a compound having an epoxy group and an unsaturated double bond in one molecule. Hydroxyl and carboxyl group-containing photosensitive resin obtained by
(7) A reaction product of a polyfunctional epoxy compound, an unsaturated monocarboxylic acid, an 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 a saturated or unsaturated polybasic acid anhydride,
(8) A polyfunctional oxetane compound having a plurality of oxetane rings in one molecule is reacted with an unsaturated monocarboxylic acid, and a saturated or unsaturated polybasic acid anhydride is bonded to the primary hydroxyl group in the resulting modified oxetane resin. A carboxyl group-containing photosensitive resin obtained by reacting a product, and (9) a carboxyl group-containing resin obtained by reacting an unsaturated monocarboxylic acid with a polyfunctional epoxy resin and then reacting with a polybasic acid anhydride. Furthermore, examples thereof include, but are not limited to, 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. .

  Among these examples, the carboxyl group-containing photosensitive resins (2) and (3) are preferable from the viewpoints 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, it is preferable that 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. If the acid value of the carboxyl group-containing resin (A) is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, if it exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds, so the line becomes thinner than necessary. In some cases, it is not preferable because the resist is dissolved and peeled off with a developer without distinction between an exposed portion and an unexposed portion, and it becomes 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 inferior. 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 blending ratio of such a carboxyl group-containing resin (A) is preferably 3 to 50% by mass, more preferably 5 to 30% by mass in the case of a conductive paste in the entire composition. In the case of, it is preferably 10 to 80% by mass, more preferably 15 to 50% by mass. When the amount is less than the above range, the coating strength is lowered, which is not preferable. On the other hand, when the amount is larger than the above range, the viscosity becomes high and the coating property and the like deteriorate, which is not preferable.

  As an inorganic component (B) used for the photosensitive composition of the present invention, (B-1) a colorant exhibiting black as a main component, (B-2) silver powder, and (B-) depending on the desired application 3) Glass powder etc. are used individually or in combination of 2 or more types.

  Regardless of which inorganic component (B) is used, it is preferable to add glass powder (B-3) in order to increase the adhesion to the substrate. As the glass powder (B-3), a low-melting glass powder having a softening point of 300 to 600 ° C. is used, and those containing lead oxide, bismuth oxide, or zinc oxide as a main component can be preferably used. Moreover, it is preferable to use a thing with an average particle diameter of 20 micrometers or less from the point of resolution, and it is more preferable to use a thing with 5 micrometers or less.

Preferred examples of the glass powder based on lead oxide (B-3), in terms of% by mass on the oxide basis, PbO is _48~82%, B 2 _{0 3} is 0.5 to 22%, SiO ₂ is Composition of ₃ to 32%, Al ₂ O ₃ of 0 to 12%, BaO of 0 to 10%, ZnO of 0 to 15%, TiO _{2 of 0} to 2.5%, Bi ₂ O ₃ of 0 to 25% And a non-crystalline frit having a softening point of 420 to 590 ° C.

Preferred examples of the glass powder based on bismuth oxide (B-3), in terms of% by mass on the oxide basis, _Bi 2 _{O 3} is _35-88%, B 2 _{O 3} 5 to 30%, SiO ₂ is 0~20%, _Al 2 _{O 3} is 0 to 5%, BaO is 1 to 25%, ZnO has from 1 to 20% of the composition, the non-crystalline frit softening point is 420-590 ° C. Is mentioned.

Furthermore, as a preferable example of the glass powder (B-3) containing zinc oxide as a main component, ZnO is 25 to 60%, K ₂ O is 2 to 15%, and B ₂ O _{3 in} mass% based on oxide. but 25 to 45% SiO ₂ is 1 to 7% _Al 2 _{O 3} is 0 to 10%, BaO is 0 to 20% MgO has a composition of 0-10%, the softening point of four hundred twenty to five hundred and ninety ° C. Non-crystalline frit that is

  (I) The inorganic component (B) used in the case where the photosensitive composition of the present invention is used for forming a fired product pattern in which black color is required, specifically, for forming a black matrix pattern or the like will be described.

  When formulating the photosensitive composition of the present invention as a black paste, a colorant (B-1) exhibiting black is used as a main component as the inorganic component (B). As the black colorant (B-1), a single metal oxide such as Cu, Fe, Cr, Mn, Co, Ru, La, and / or a composite oxide composed of two or more metal elements is preferably used. be able to. In addition, in the present invention, the colorant (B-1) exhibiting black includes, in addition to a colorant exhibiting black alone, a colorant as a combination exhibiting black by mixing two or more chromatic colors.

  In the present invention, the average particle diameter of the black colorant (B-1) is preferably 10 μm or less, more preferably 2.5 μm or less from the viewpoint of resolution. On the other hand, in terms of blackness, those having an average particle size of 1.0 μm or less, preferably 0.6 μm or less are suitable.

Among such colorants (B-1) exhibiting black color, 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. 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 rate of the coloring agent (B-1) which exhibits black, the range of 10-100 mass parts per 100 mass parts of said carboxyl group-containing resin (A) is suitable. When the amount is less than the above range, it is not preferable because sufficient blackness cannot be obtained after firing. On the other hand, when the amount is larger than the above range, the light transmittance is lowered, and an undercut is likely to occur.

  (Ii) Next, the photosensitive composition of the present invention is an inorganic component used in the case where the fired product pattern is required to have conductivity, specifically for use in forming a conductive pattern such as an electrode. (B) will be described.

  When formulating the photosensitive composition of the present invention as a conductive paste, silver powder (B-2) is used as a main component for imparting conductivity to the paste as the inorganic component (B). As for the silver powder (B-2), it is preferable to use a silver powder (B-2) having a half value width of an Ag (111) plane peak in an X-ray analysis pattern of 0.15 ° or more, preferably 0.19 ° or more. From the aspect, it is preferable. This silver powder (B-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, so that 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 (B-2) is low, the binding between the particles proceeds too much, and there is a risk of irregular undulation or twisting of the line.

  Such silver powder (B-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 (B-2) thus obtained can be used in various shapes such as a spherical shape, a flake shape, and a dentlite shape, but a spherical shape should be used particularly considering optical characteristics and dispersibility. Is preferred.

  Moreover, this silver powder (B-2) is an average particle diameter of ten random silver powders observed at 10,000 times using an electron microscope (SEM), and is 0.1 to 5 μm, preferably 0.00. 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.

Furthermore, it is preferable to use silver powder (B-2) having 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 blending ratio of such silver powder (B-2) is suitably 50 to 90 parts by mass with respect to 100 parts by mass of the photosensitive composition of the present invention. When the blending ratio of the silver powder (B-2) is less than the above range, sufficient conductivity of the conductive pattern obtained from the paste cannot be obtained. On the other hand, when the amount exceeds the above range, This is not preferable because the adhesiveness deteriorates.

  (Iii) In addition, when the photosensitive composition of the present invention is used for applications where the fired product pattern is required to be black and conductive, specifically for forming a black layer of a bus electrode, When formulating the photosensitive composition as a conductive black paste, the colorant (B-1) and silver powder (B-2) exhibiting the black color are used as the main components as the inorganic component (B).

  As described above, the colorant (B-1) and / or silver powder (B-2) exhibiting a black color is blended as the main component of the inorganic component (B) and the photosensitive composition is formulated. The glass powder (B-3) is preferably added in order to improve the strength of the subsequent film and the adhesion to the substrate. The blending ratio is preferably 1 to 40 parts by mass, more preferably 2 to 20 parts by mass in the entire composition. 1 mass part or more is preferable from a viewpoint of the adhesive improvement effect with a base material, and on the other hand, when it exceeds 40 mass parts, there exists a possibility that the thickening and gelatinization of a composition may be produced, it is not preferable.

  (Iv) Further, when the photosensitive composition of the present invention is formulated as a glass paste for partition pattern formation, the glass powder (B-3) is used as a main component as the inorganic component (B). .

  In addition, the boric acid and / or phosphorus compound which are mentioned later can also be added to the photosensitive composition of this invention for storage stability improvement.

Examples of the compound (C) having a radically polymerizable unsaturated group used in the present invention include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate; Mono- or diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol; acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide, N, N-dimethylaminopropylacrylamide; N, Aminoalkyl acrylates such as N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; hexanedio , Trimethylolpropane, pentaerythritol, dipentaerythritol, polyhydric alcohols such as tris-hydroxyethyl isocyanurate, or polyhydric acrylates such as these ethylene oxide adducts or propylene oxide adducts; phenoxy acrylate, bisphenol A diacrylate Acrylates such as ethylene oxide or propylene oxide adducts of these phenols; acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate; Polyfunctional or monofunctional polyurea which is an isocyanate modification of the above hydroxyalkyl acrylate Emissions acrylate; and melamine acrylate, and / or the like each methacrylates corresponding to the acrylates and the like, which may be used alone or in combination of two or more. Of these, compounds having a plurality of 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 (C).

  The compounding ratio of the compound (C) having such a radical polymerizable unsaturated group is preferably 5 to 100 parts by mass, more preferably 10 to 70 parts with respect to 100 parts by mass of the carboxyl group-containing resin (A). It is a ratio of parts by mass. When the blending ratio is less than 5 parts by mass, the photocurability is lowered, 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 exceeds 100 parts by mass, the solubility in an alkaline aqueous solution is lowered or the coating film becomes brittle, which is not preferable.

  In order to solve the problems of the present invention, it is important to use a liquid phosphine oxide photopolymerization initiator (D-1) as the photopolymerization initiator (D) used in the photosensitive composition of the present invention. . In other words, conventionally used photopolymerization initiators have low solubility in solvents, and even when the appearance is uniform as a paste by refrigerated storage, the photopolymerization initiator crystallizes out, resulting in defects in the pattern formed. As a result, when a liquid photopolymerization initiator was used at room temperature, it was possible to obtain a good pattern free from defects such as pinholes and chipped lines. In addition, a large amount of solvent used for dissolving a compound having low solubility is unnecessary in the present invention, which is preferable from the viewpoint of reducing environmental load.

As the liquid phosphine oxide photopolymerization initiator (D-1), in particular, the following general formula (I):

(Wherein R ¹ is a linear or branched alkyl group having 1 to 12 carbon atoms, and R ² is substituted with a cyclohexyl group, a cyclopentyl group, an aryl group, a halogen atom, an alkyl group or an alkoxy group. An aryl group, or a carbonyl group having 1 to 20 carbon atoms.)
It is preferable to have a structure represented by

  In the present invention, liquid means liquid at room temperature. Room temperature refers to 10 to 40 ° C., and liquid at room temperature refers to a temperature range of 10 to 40 ° C. When a sample is placed in a test tube with an inner diameter of 30 mm up to a height of 55 mm and the test tube is leveled, 85 mm from the bottom. It means a state within 90 seconds until it passes through the part. Specifically, ethyl-2,4,6-trimethylbenzoylphenylphosphinate or the like is suitably used as such a liquid phosphine oxide photopolymerization initiator (D-1) at room temperature.

  In the present invention, the liquid phosphine oxide photopolymerization initiator (D-1) includes not only a compound that is liquid at room temperature but also a phosphine that is liquid at room temperature as a mixture of a solid compound and a liquid compound at room temperature. An oxide polymerization initiator is also included. Specifically, ethyl-2,4,6-trimethylbenzoylphenylphosphinate that is liquid at room temperature and 2,4,6-trimethylbenzoyldiphenylphosphine oxide or bis (2,4,6-trimethylbenzoyl) phenylphosphine Those liquefied by mixing with a phosphine oxide photopolymerization initiator that is solid at room temperature, such as oxide, can also be used. The mixing ratio is preferably 70 to 98% by mass of a phosphine oxide-based photopolymerization initiator that is liquid at room temperature, and 2 to 30% by mass of a phosphine oxide-based polymerization initiator that is solid at room temperature.

  The blending ratio of the liquid phosphine oxide photopolymerization initiator (D-1) is preferably 0.5 to 40 parts by mass in the case of a conductive paste with respect to 100 parts by mass of the carboxyl group-containing resin (A). More preferably, it is 1-20 mass parts, In the case of a nonelectroconductive paste, Preferably it is 0.5-60 mass parts, More preferably, it is 1-50 mass parts. When the mixing ratio of the phosphine oxide photopolymerization initiator (D-1) is less than the above range, it is not preferable because sufficient curability cannot be obtained. On the other hand, when it exceeds the above range, the thick film curability is lowered. However, this is not preferable because it leads to an increase in the cost of the product.

In order to further increase the sensitivity of the photosensitive composition of the present invention, it is preferable to use an oxime photopolymerization initiator (D-2) in combination as the photopolymerization initiator (D). As the oxime photopolymerization initiator (D-2), the following general formula (IV):

(In the formula, one or two R ^{1 s} are represented by the following general formula (V), and the remaining R ¹ represents a hydrogen atom, a methyl group, an ethyl group, a phenyl group, or a halogen atom.)

(In the formula, R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
The compound represented by these can be used.

Examples of such a compound include the following formula (VI):

2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the above, and a commercially available product is CGI-325 manufactured by Ciba Specialty Chemicals.

  As the oxime-based photopolymerization initiator (D-2), in addition to the above compounds, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (Ciba Specialty) Chemicals, trade name Irgacure OXE01), Ethanone, 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (Ciba Also available from Specialty Chemicals, trade name Irgacure OXE02).

  As a compounding rate of such an oxime system photoinitiator (D-2), 0.05-10 mass parts is preferable with respect to 100 mass parts of said carboxyl group-containing resin (A), 0.1-5 Part by mass is more preferable. When the blending ratio of the oxime photopolymerization initiator (D-2) is less than 0.05 parts by mass, it is difficult to further increase the sensitivity, which is not preferable. On the other hand, when the amount exceeds 10 parts by mass, the thick film curability is lowered and the cost of the product is increased.

  Further, the blending ratio of the oxime photopolymerization initiator (D-2) is less than the blending ratio of the liquid phosphine oxide photopolymerization initiator (D-1) containing the structure represented by the general formula (I). Is preferable in order to obtain thick film curability with high sensitivity. The blending ratio is [D-2] / [D-2] / [D-2] when the blending ratio of the oxime photopolymerization initiator = [D-2] and the blending ratio of the phosphine oxide photopolymerization initiator = [D-1]. D-1] is desirably in the range of 1/2 to 1/40 in the case of the conductive paste and 1/2 to 1/60 in the case of the non-conductive paste. When [D-2] / [D-1] exceeds the above range, it becomes difficult to obtain sufficient deep curability due to the influence of the oxime photopolymerization initiator (D-2). The case is not preferable from the viewpoint of increasing sensitivity.

  The photosensitive composition of the present invention further includes benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether within the range in which crystal precipitation does not occur due to low-temperature storage if necessary; acetophenone Acetophenones such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; 2-methyl-1 Aminoacetophenones such as-[4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; Methyl anthraquinone, 2-ethyl Anthraquinones such as anthraquinone, 2-tertiarybutylanthraquinone, 1-chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; acetophenone dimethyl Ketals such as ketal and benzyldimethyl ketal; benzophenones such as benzophenone; or xanthones; (2,6-dimethoxybenzoyl) -2,4,4-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -Photopolymerization initiators such as phosphine oxides such as phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide may be used in combination. In particular, it is preferable to use a thioxanthone-based photopolymerization initiator such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone from the viewpoint of deep curability.

  In addition, it is preferable to add boric acid and / or a phosphorus compound to the photosensitive composition of the present invention in order to increase storage stability.

  Such boric acid has an average particle size (D50) pulverized by a jet mill, ball mill, roll mill or the like, preferably 20 μm or less, more 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.

  0.01-10 mass parts is suitable with respect to 100 mass parts of said glass powder (B-3), and, as for the compounding ratio of such a boric acid, Preferably, it is 0.1-2 mass parts. If the blending ratio of boric acid is less than 0.01 parts by mass with respect to 100 parts by mass of the glass powder (B-3), there is no effect of improving storage stability, which is not preferable.

  In addition, when boric acid is blended in this way, it is desirable 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, the water dissolved in the organic solvent ionizes the metal contained in the glass powder (B-3) and causes gelation, which is not preferable.

Moreover, as a phosphorus compound, following formula (II) or formula (III):

It is preferable to incorporate a phosphorus compound having a structure represented by:

  Examples of such phosphorus compounds include methyl phosphate, ethyl phosphate, propyl phosphate, butyl phosphate, phenyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dipropyl phosphate, diphenyl phosphate, and phosphoric acid. Isopropyl, 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 phosphate, mono (2-methacryloyl) Oxyethyl) acid phosphate, mono (2-acryloyloxy) Chill) acid phosphate, di (2-methacryloyloxyethyl) acid phosphate, di (2-acryloyloxyethyl) acid phosphate, ethyl diethylphosphonoacetate, 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.

  The mixing ratio of these phosphorus compounds is preferably 10 parts by mass or less, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the glass powder (B-3). Since the calcination property falls when the compounding rate of a phosphorus compound exceeds 10 mass parts with respect to 100 mass parts of the said glass powder (B-3), it is unpreferable.

  In the photosensitive composition of the present invention, an organic solvent can be used for the synthesis of the carboxyl group-containing resin (A), the preparation 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 And 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.

  In addition, as mentioned above, when boric acid is blended, it is desirable to use a hydrophobic solvent having a solubility in 100 g of water at 25 ° C. of 20 g or less.

  The photosensitive composition of the present invention may further comprise, if necessary, a thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, a thickener such as fine silica, organic bentonite, montmorillonite, silicone Known and commonly used additives such as antifoaming agents and / or leveling agents such as fluorinated and polymeric materials, and silane coupling agents such as imidazole, thiazole and triazole can be blended.

  The photosensitive 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, a dip coating method, a flow coating method, a roll coating method, a bar coater method, a die coating is used. A tack-free coating film can be formed by coating by a method such as a method, a screen printing method, or a curtain coating method, and drying 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 film thickness of the coating film dried in this way is 0.01-0.8. When the absorbance is less than 0.01, the coating film is insufficiently absorbed by the light and it is difficult to form an image, which is not preferable. On the other hand, when the absorbance exceeds 0.8, it is not preferable because the deep curability is lowered and the pattern shape tends to be in an undercut state. Furthermore, when the colorant (B-1) exhibiting black is included as the inorganic component (B), the absorbance is more preferably 0.1 to 0.8, and the colorant (B-1) exhibiting black. When it does not contain, the absorbance is more preferably 0.01 to 0.4. In order to adjust the range of absorbance to 0.01 to 0.8, liquid phosphine oxide photopolymerization initiator (D-1), oxime photopolymerization initiator (D-2), inorganic component (B) This can be dealt with by adjusting the amount added.

  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 pattern is 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. Moreover, it is preferable to perform washing with water and acid neutralization in order to remove an unnecessary developer after development.

  The substrate patterned by the above development can be formed into various desired patterns by baking at about 400 to 600 ° C. in air or in a nitrogen atmosphere.

  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 (A-1 varnish) In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, methyl methacrylate and methacrylic acid were added in a molar ratio of 0.87: 0.13. Then, dipropylene glycol monomethyl ether as a solvent and azobisisobutyronitrile as a catalyst were added and stirred at 80 ° C. for 6 hours in 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 the Shimadzu Corporation pump LC-6AD and Showa Denko Co., Ltd. column Shodex (registered 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 (A-2 varnish) 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 set at a molar ratio of 0. 76: 0.24, dipropylene glycol monomethyl ether as a solvent and azobisisobutyronitrile as a catalyst were added and stirred at 80 ° C. for 6 hours in 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. In addition, the said weight average molecular weight was measured using the method similar to the measuring method of the weight average molecular weight in the copolymer resin of A-1 varnish.

(I) Black paste composition Examples 1-8 and Comparative Examples 1-2
The compounding components shown in Table 1-1 using the A-1 varnish and A-2 varnish obtained in the synthesis example were kneaded with a three-roll mill to obtain a black paste composition.

(Ii) Silver paste composition Examples 9-16 and Comparative Examples 3-4
The compounding components shown in Table 1-2 using the A-1 varnish and A-2 varnish obtained in the above synthesis example were kneaded with a three-roll mill to obtain a silver paste composition.

(Iii) Black silver paste compositions Examples 17-24 and Comparative Examples 5-6
The compounding components shown in Table 1-3 using the A-1 varnish and A-2 varnish obtained in the above synthesis example were kneaded with a three-roll mill to obtain a black silver paste composition.

[1] Various paste compositions of Examples 1 to 24 and Comparative Examples 1 to 6 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. Then, CAD data in a stripe shape (black paste: line width (L) 100 μm, space width (S) 150 μm; silver paste: L / S = 50/200 μm; black silver paste: L / S = 50/200 μm) is used. In 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, the integrated light amount on the composition is 40 mJ / cm ² for black paste and silver paste. The black silver paste was exposed to 100 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.

The results of evaluating the various characteristics of the substrates thus obtained are shown in Tables 2-1 to 2-3 and Tables 3-1 to 3-3.
The evaluation methods in these tables are as follows.

(1) Evaluation of storage stability After the various paste compositions obtained were stored in a freezer at -20 ° C for 7 days, they were applied and dried on a glass substrate, the surface state was visually observed, and crystals of the photopolymerization initiator were observed. It was evaluated whether or not there was a foreign substance due to precipitation.

○: A smooth coating film is formed, and no foreign matter due to crystal precipitation of the initiator is observed. Δ: A foreign matter due to crystal precipitation of the initiator exists in a part of the coating film. (2) Absorbance measurement The absorbance of the evaluation substrate on which 5 μm and 10 μm dry film thicknesses are formed on soda lime glass is measured by UV-visible spectrophotometry. Measured using a meter. From the obtained data, the absorbance per 1 μm thickness at 405 nm was calculated.

(3) Laser sensitivity evaluation line (black paste: L / S = 100/150 μm; silver paste: L / S = 50/200 μm; black silver paste: L / S = 50/200 μm) The black paste and silver paste were exposed to 50 mJ / cm ² , and the black silver paste was 100 mJ / cm ^2, and developed for 20 seconds using a 0.4 mass% Na ₂ CO ₃ aqueous solution at a liquid temperature of 30 ° C. It was evaluated whether a line could be formed with a microscope.

The evaluation criteria are as follows.
○: No defect is observed at all.
Δ: Some defects are observed.
X: A line cannot be formed.

(4) Calculation of minimum exposure amount Exposure is performed by changing the integrated light amount, and a line (black paste: L / S = 100/150 μm, silver paste: L / S = 50/200 μm, or black silver paste: L / S = 50/200 μm) was measured for the minimum exposure that can be formed without defects. Since the comparative example was not practical because the exposure time with a laser was long, the subsequent test was not performed. In Comparative Example 5, no image could be formed with a laser beam having a center wavelength of 405 nm.

(5) Line shape after pattern formation The pattern after development in various paste compositions of the alkali development type 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.

(6) 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.

(7) Adhesiveness Adhesiveness was evaluated by peeling with a cellophane 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.

(8) Measurement of specific resistance value About silver paste composition (Examples 9-16, comparative examples 3-4) and black silver paste composition (Examples 17-24, comparative examples 5-6), specific resistance The value was measured.

A test substrate was produced in the same manner as 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 clear from the results shown in Tables 2-1 to 2-3, the black paste composition, the silver paste composition, and the black silver paste composition of the present invention are all stably stored without crystal precipitation due to low-temperature storage. It turns out that it is excellent in property.

  As is clear from the results shown in Tables 3-1 to 3-3, it can be seen that the various paste compositions of the present invention have sufficient sensitivity to laser light and can form high-definition patterns. Moreover, it turns out that a sensitivity improves further by using together with an oxime system photoinitiator (D-2), and it becomes a more useful thing for laser exposure. Furthermore, the various paste compositions of the present invention were free from irregular variations in the line shape after firing, and were excellent in adhesion to the substrate. In addition, about the black paste composition of this invention, the blackness after baking can also be satisfied, and the specific resistance value is sufficient as an electrode material about the silver paste composition and black silver paste composition of this invention. there were.

[2] Subsequently, pattern formation by lamp-type exposure was also performed. The paste compositions of Examples 1 to 24 and Comparative Examples 1 to 6 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, a glass dry plate on which a negative pattern of stripes (black paste: L / S = 100/150 μm; silver paste: L / S = 50/200 μm; black silver paste: L / S = 50/200 μm) was formed Using an exposure apparatus (MAT-5301, manufactured by Hakuto Co., Ltd.), which is used as a mask and equipped with an ultrahigh pressure mercury lamp as a light source, the integrated light quantity on the glass dry plate is 50 mJ / cm ² for black paste and silver paste, and 100 mJ / for black silver paste. It was exposed so as to be 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 in a process of 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.

  The results of evaluating the various characteristics of each substrate thus obtained are shown in Tables 4-1 to 4-3. The evaluation methods in these tables are as follows.

(9) Photosensitivity evaluation in lamp type exposure (Black paste: L / S = 100/150 μm; Silver paste: L / S = 50/200 μm; Black silver paste: L / S = 50/200 μm) Integration Exposure is performed so that the amount of light is 50 mJ / cm ² for black paste and silver paste, and 100 mJ / cm ² for black silver paste, and development is performed for 20 seconds using a 0.4 mass% Na ₂ CO ₃ aqueous solution at 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.

(10) Calculation of minimum exposure amount Exposure is performed by changing the integrated light amount, and a line (black paste: L / S = 100/150 μm, silver paste: L / S = 50/200 μm, or black silver paste: L / S = 50/200 μm) was measured for the minimum exposure that can be formed without defects.

(11) Line shape after pattern formation The pattern after development in various paste compositions of the alkali development type 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.

(12) 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.

(13) 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.

(14) Measurement of specific resistance value About silver paste composition (Examples 9-16, Comparative Examples 3-4) and black silver paste composition (Examples 17-24, Comparative Examples 5-6), specific resistance The value was measured.
A test substrate was produced in the same manner as 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 Tables 4-1 to 4-3, the various alkali-developable paste compositions of the present invention have sufficient sensitivity even when an ultra-high pressure mercury lamp (lamp exposure) is used as a light source. It was found that a high-definition pattern can be formed. In addition, since the sensitivity has been dramatically improved, the exposure time can be significantly reduced when applied to the conventional lamp type exposure. Furthermore, there was no irregular variation in the line shape after firing, good adhesion to the substrate, and excellent storage stability. Regardless of the exposure method, the black paste composition of the present invention can satisfy the blackness after firing, and the silver paste composition and black silver paste composition of the present invention have a specific resistance value. Was sufficient as an electrode material.

Claims (8)

  An alkali developing type containing (A) a carboxyl group-containing resin, (B) an inorganic component, (C) a compound having a radical polymerizable unsaturated group, and (D-1) a liquid phosphine oxide photopolymerization initiator. Photosensitive composition.   (A) a carboxyl group-containing resin, (B) an inorganic component, (C) a compound having a radical polymerizable unsaturated group, (D-1) a liquid phosphine oxide photopolymerization initiator, and (D-2) an oxime An alkali development type photosensitive composition containing a photopolymerization initiator.   The alkali developing type according to claim 1 or 2, wherein the inorganic component (B) is selected from (B-1) a colorant exhibiting black color, (B-2) silver powder, and (B-3) glass powder. Photosensitive composition. 4. The alkali developing type according to claim 1, wherein the phosphine oxide photopolymerization initiator (D-1) includes a structure represented by the following general formula (I): Photosensitive composition.

In the formula, R ¹ is a linear or branched alkyl group having 1 to 12 carbon atoms, and R ² is substituted with a cyclohexyl group, a cyclopentyl group, an aryl group, a halogen atom, an alkyl group or an alkoxy group. An aryl group or a C1-C20 carbonyl group is represented.   The mixing ratio of the oxime photopolymerization initiator (D-2) is smaller than the mixing ratio of the phosphine oxide photopolymerization initiator (D-1). The alkali development type photosensitive composition as described in 1.   The absorbance per 1 μm film thickness of the coating film obtained by diluting the photosensitive composition according to any one of claims 1 to 5 with an organic solvent and coating and drying is 0.01 to 0.8. An alkali developing type photosensitive composition characterized by the above.   The pattern which consists of a baked product of the photosensitive composition of Claim 1 or 2.   The pattern according to claim 7, comprising an inorganic component (B) selected from (B-1) a colorant exhibiting black color, (B-2) silver powder, and (B-3) glass powder. .