KR101451986B1 - Photosensitive composition and pattern comprising calcined material thereof - Google Patents
Photosensitive composition and pattern comprising calcined material thereof Download PDFInfo
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- KR101451986B1 KR101451986B1 KR1020080044023A KR20080044023A KR101451986B1 KR 101451986 B1 KR101451986 B1 KR 101451986B1 KR 1020080044023 A KR1020080044023 A KR 1020080044023A KR 20080044023 A KR20080044023 A KR 20080044023A KR 101451986 B1 KR101451986 B1 KR 101451986B1
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- 0 *c(c(*)c1*)c(*)c2c1Sc(c(*)c(*)c(*)c1*)c1C2=O Chemical compound *c(c(*)c1*)c(*)c2c1Sc(c(*)c(*)c(*)c1*)c1C2=O 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B55/00—Azomethine dyes
- C09B55/002—Monoazomethine dyes
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133512—Light shielding layers, e.g. black matrix
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Optics & Photonics (AREA)
- Materials For Photolithography (AREA)
- Liquid Crystal (AREA)
- Optical Filters (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Polymerisation Methods In General (AREA)
- Gas-Filled Discharge Tubes (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
An object of the present invention is to provide an alkali developing type photosensitive composition capable of effectively suppressing occurrence of defects such as pinholes or line defects that occur during patterning. Further, it is intended to provide a pattern free from defects such as pinholes or line defects including a fired product of the composition.
The photosensitive composition for an alkali developing type of the present invention comprises (A) a resin containing a carboxyl group, (B) an inorganic component, (C) a compound having a radically polymerizable unsaturated group, and (D-1) a liquid phase phosphine oxide- do.
Photosensitive composition, pattern
Description
The present invention relates to a photosensitive composition suitable for forming a black matrix pattern, a conductive pattern, a barrier rib pattern and the like in various thin type displays such as a plasma display panel, a field emission display, a liquid crystal display and the like, and a pattern containing the fired product thereof.
In the thin type display, various patterns such as a black matrix pattern, a conductive pattern (electrode circuit), and a barrier rib pattern are used. As a method of forming the resist pattern, for example, a resist for forming a pattern is coated on a glass substrate and dried to form a coating film. The coated film is exposed to light through a photomask on which a circuit or an electrode pattern is drawn, , A resist layer corresponding to a circuit or an electrode pattern is formed and fired to form a pattern adhered to the glass substrate.
Recently, a laser direct imaging (hereinafter referred to as LDI) method in which a circuit formed by CAD (Computer Aided Design) is directly drawn by a laser beam has been recognized. Since the LDI draws the pattern directly from the CAD data, it is possible not only to efficiently produce a small quantity of various items but also to use the photomask, so that the alignment is accurate, the scaling is easily corrected, Various photoresist paste compositions suitable for the above patterning method have been developed (see, for example, Patent Documents 1 to 3 below), since there is no need to control adhesion, contamination, and damage of foreign materials to the substrate .
However, even in the case of using any patterning method, it is difficult to eliminate defects such as pinholes, line defects, line shorts, line open defects, and the like that occur during patterning. Therefore, Development of a composition is required.
[Patent Document 1] Japanese Unexamined Patent Application Publication No. 2002-351071 (Claims)
[Patent Document 2] Japanese Unexamined Patent Application Publication No. 2002-351072 (Claims)
[Patent Document 3] Japanese Patent Application Laid-Open No. 2004-45596 (Claims)
It is an object of the present invention to provide an alkali developing photosensitive composition capable of effectively suppressing the occurrence of defects such as pinholes and line defects that are generated during patterning, It is an object of the present invention to provide a pattern including defects such as pinholes and lines.
As a result of intensive studies to achieve the above object, it has been found that crystal precipitation of an additive photopolymerization initiator occurs even when the appearance is uniform as a paste due to cooling during storage, and this causes a defect in the case of forming a coating film .
That is, the present invention provides, in a first aspect thereof, a process for producing a photoresist composition which comprises (A) a carboxyl group-containing resin, (B) an inorganic component, (C) a compound having a radically polymerizable unsaturated group, and (D-1) a liquid phase phosphine oxide- Sensitive photosensitive composition of the present invention.
According to one embodiment of the present invention, the inorganic component (B) is selected from (B-1) black coloring agent, (B-2) silver powder and (B-3) glass powder.
Further, according to another aspect of the present invention, the liquid phase phosphine oxide-based photopolymerization initiator (D-1) includes a structure represented by the following formula (I).
(I)
(Wherein R 1 is a linear or branched alkyl group having 1 to 12 carbon atoms and R 2 is an aryl group substituted with a cyclohexyl group, a cyclopentyl group, an aryl group, a halogen atom, an alkyl group or an alkoxy group, Lt; / RTI > to 20 carbon atoms)
Further, in another embodiment of the present invention, the compounding ratio of the oxime-based photopolymerization initiator (D-2) is lower than that of the phosphine oxide-based photopolymerization initiator (D-1).
Further, in another aspect of the present invention, the photosensitive composition of the present invention is diluted with an organic solvent and has an absorbance of 0.01 to 0.8 per 1 m of the film thickness of the coated and dried film.
In a second aspect, the present invention provides a pattern comprising a fired product of the photosensitive composition.
In the photosensitive composition of the present invention in which the liquid phase phosphine oxide-based photopolymerization initiator (D-1) is used as the photopolymerization initiator, crystallization of the photopolymerization initiator does not occur due to low-temperature storage, Foreign matter that may cause defects is not present in the paste after cooling. Therefore, according to the present invention, it becomes possible to provide various pattern fired products free from defects such as pinholes and line defects.
The photosensitive composition of the present invention is an alkali developing type photosensitive resin composition containing (A) a carboxyl group-containing resin, (B) an inorganic component, (C) a compound having a radically polymerizable unsaturated group, and (D-1) a liquid phase phosphine oxide- , And in a preferred embodiment, the liquid phase phosphine oxide-based photopolymerization initiator (D-1) comprises the structure represented by the above formula (I).
Hereinafter, each component of the photosensitive composition of the present invention will be described 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. In addition, a carboxyl group-containing photosensitive resin (A ') having a radically polymerizable unsaturated double bond in the molecule is more preferable in terms of photocurability and resistance to development.
Specifically, resins listed below can be mentioned.
(1) a carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid with at least one compound other than the unsaturated double bond,
(2) a copolymer of an unsaturated carboxylic acid such as (meth) acrylic acid with at least one compound other than the unsaturated double bond, glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl A carboxyl group-containing photosensitive resin obtained by adding an ethylenically unsaturated group as a pendant with a compound having an epoxy group and an unsaturated double bond such as (meth) acrylate or (meth) acrylic acid chloride,
(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 the above A carboxyl group-containing photosensitive resin obtained by reacting a polyvalent carboxylic acid anhydride with an unsaturated carboxylic acid such as (meth) acrylic acid, and reacting the produced secondary hydroxyl group with a polybasic acid anhydride,
(4) An unsaturated double bond is added to a copolymer of an acid anhydride having an unsaturated double bond such as maleic anhydride and a compound having another unsaturated double bond, such as 2-hydroxyethyl (meth) A carboxyl group-containing photosensitive resin obtained by reacting a compound having a carboxyl group,
(5) a carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting the resulting hydroxyl group with a saturated or unsaturated polybasic acid anhydride,
(6) a method of reacting a saturated or unsaturated polybasic acid anhydride with a hydroxyl group-containing polymer such as a polyvinyl alcohol derivative, and then reacting the resultant carboxylic acid with a compound having an epoxy group and an unsaturated double bond in a molecule to give a photosensitive resin containing a hydroxyl group and a carboxyl group ,
(7) A polyfunctional epoxy compound obtained by reacting a reaction product of a polyfunctional epoxy compound, an unsaturated monocarboxylic acid and a compound having one reactive group other than an alcoholic hydroxyl group and an alcoholic hydroxyl group reactive with an epoxy group in one molecule with a saturated or unsaturated polybasic acid anhydride A carboxyl group-containing photosensitive resin,
(8) A method for producing a carboxyl-containing compound, which comprises reacting a polyfunctional oxetane compound having a plurality of oxetane rings in a molecule with an unsaturated monocarboxylic acid and reacting a saturated or unsaturated polybasic acid anhydride with the primary hydroxyl group in the obtained modified oxetane resin Photosensitive resin and
(9) reacting a polyfunctional epoxy resin with an unsaturated monocarboxylic acid, and then reacting the polyfunctional epoxy resin with a polybasic acid anhydride, with a compound having one oxirane ring and at least one ethylenic unsaturated group in the molecule And a carboxyl group-containing photosensitive resin to be obtained. However, the present invention is not limited thereto.
Among these examples, the carboxyl group-containing photosensitive resin of (2) and (3) is preferable from the viewpoints of photo-curability and plasticity.
In the present specification, the term (meth) acrylate is generically referred to as 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 alkaline solution becomes possible.
The acid value of the carboxyl group-containing resin (A) is preferably in the range of 40 to 200 mgKOH / g, more preferably in the range of 45 to 120 mgKOH / g. If the acid value of the carboxyl group-containing resin (A) is less than 40 mgKOH / g, the alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed portion by the developer proceeds, Therefore, it is not preferable because it is dissolved and peeled off as a developing solution without distinguishing between the exposed portion and the unexposed portion, rendering normal resist pattern drawing difficult.
The weight average molecular weight of the carboxyl group-containing resin (A) varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. If the weight average molecular weight is less than 2,000, the tack-free performance may deteriorate, and the moisture resistance of the coated film after exposure may deteriorate, resulting in film reduction during development, resulting in a significant decrease in resolution. On the other hand, if the weight average molecular weight exceeds 150,000, the developability may be markedly deteriorated, and the storage stability may be lowered.
The blending ratio of the carboxyl group-containing resin (A) in the composition is preferably 3 to 50 mass%, more preferably 5 to 30 mass% in the case of the conductive paste, and preferably 10 to 80 mass %, More preferably from 15 to 50 mass%. If it is less than the above range, the coating film strength is undesirably lowered. On the other hand, when the amount is larger than the above range, the viscosity is increased or the coating property is lowered.
As the inorganic component (B) to be used in the photosensitive composition of the present invention, a colorant showing (B-1) black, (B-2) silver powder and (B-3) They may be used alone or in combination of two or more.
In the case of using any inorganic component (B), it is preferable to add the glass powder (B-3) in order to improve adhesion with the substrate. As the glass powder (B-3), a low-melting-point glass powder having a softening point of 300 to 600 ° C is used, and it is preferable to use a glass powder containing oxides, bismuth oxide or zinc oxide as a main component. In terms of resolution, it is preferable to use one having an average particle diameter of 20 탆 or less, more preferably 5 탆 or less.
Preferred examples of the glass powder (B-3) containing oxide lead as a main component include PbO in an amount of 48 to 82%, B 2 O 3 in an amount of 0.5 to 22%, SiO 2 in an amount of 3 to 32%, Al 2 O 3 having a composition of 0 to 12%, BaO of 0 to 10%, ZnO of 0 to 15%, TiO 2 of 0 to 2.5% and Bi 2 O 3 of 0 to 25% and a softening point of 420 to 590 ° C Amorphous frit.
Further, preferred examples of the glass powder (B-3) as a main component of bismuth oxide, in% by weight of oxide based on Bi 2 O 3 is 35 to 88%, B 2 O 3 is 5 to 30%, SiO 2 0 to Amorphous frit having a composition of 20 to 20%, Al 2 O 3 of 0 to 5%, BaO of 1 to 25% and ZnO of 1 to 20%, and a softening point of 420 to 590 ° C.
Preferable examples of the glass powder (B-3) containing zinc oxide as a main component include 25 to 60% of ZnO, 2 to 15% of K 2 O, 25 to 45% of B 2 O 3 , , Amorphous frit having a composition of 1 to 7% of SiO 2 , 0 to 10% of Al 2 O 3 , 0 to 20% of BaO and 0 to 10% of MgO, and a softening point of 420 to 590 ° C .
(i) An inorganic component (B) used in the case where the photosensitive composition of the present invention is used for forming a black matrix pattern or the like in which a black color is required in the fired pattern thereof.
When the photosensitive composition of the present invention is formulated as a black paste, a colorant (B-1) that exhibits black as the inorganic component (B) is used as the main component. As the colorant (B-1) showing black color, it is preferable to use a single metal oxide such as Cu, Fe, Cr, Mn, Co, Ru or La and / or a composite oxide containing two or more metal elements. The colorant (B-1) showing black in the present invention includes not only a colorant showing black but also a colorant as a combination of two or more kinds of chromatic colors mixed to exhibit black.
In the present invention, the average particle diameter of the coloring agent (B-1) that exhibits black is preferably 10 m or less, more preferably 2.5 m or less in terms of resolution. On the other hand, in terms of blackness, it is preferable that the average particle diameter is 1.0 占 퐉 or less, preferably 0.6 占 퐉 or less.
Among these colorants (B-1), it is 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 for this is that if the specific surface area is less than 1.0 m 2 / g, the accuracy of pattern formation by exposure is lowered, and the linearity of the line edge or the plastic film with sufficient blackness becomes difficult to obtain. On the other hand, if it exceeds 20 m < 2 > / g, the surface area of the particles becomes too large and undercuts tend to occur during development.
The blending ratio of the coloring agent (B-1) that exhibits black is suitably in the range of 10 to 100 parts by mass per 100 parts by mass of the carboxyl-containing resin (A). If it is less than the above range, sufficient blackness can not be obtained after firing, which is not preferable. On the other hand, if it is larger than the above range, the light transmittance is lowered and undercuts tend to occur, which is not preferable.
(ii) Next, the photosensitive composition of the present invention will be described with respect to an inorganic component (B) which is used for forming a conductive pattern, such as an electrode or the like, in which the fired pattern is required to have conductivity.
When the photosensitive composition of the present invention is formulated as a conductive paste, silver (B-2) is used as the main component as the inorganic component (B) in order to impart conductivity to the paste. It is preferable that the silver (B-2) has a half-width of the peak of the Ag (111) plane in the X-ray analysis pattern of 0.15 or more, preferably 0.19 or more. In the silver (B-2) having a half-value width less than 0.15, the degree of crystallization of silver is high, sintering between the particles is difficult to occur, and the resistance value is not lowered at a firing temperature of 620 占 폚 or less. The half-value width is preferably 1.0 DEG or less. If the half-value width is more than 1.0, the degree of crystallinity of the silver powder (B-2) is low and binding between particles progresses, which may cause irregular curling or entanglement of the lines.
Such silver (B-2) is generally produced by a method such as a spraying method or a chemical reduction method. The spraying method is a method in which molten silver is sprayed by a fluid such as gas or water to obtain a silver powder, spherical particles are easily obtained, and mass production is excellent. In the chemical reduction method, a water-soluble silver salt is chemically reacted with a reducing agent to obtain a silver powder. Specifically, silver nitrate is used as a water-soluble silver salt, metal silver is precipitated by using a base such as caustic alkali, ammonium salt or hydrazine as a reducing agent, and then the obtained silver slurry is washed with water and dried to obtain a silver powder.
The silver (B-2) thus obtained may have various shapes such as spherical, flaky, and dendritic shapes, but it is preferable to use spherical ones in consideration of optical characteristics and dispersibility.
The silver powder (B-2) is an average particle size of 10 random silver particles observed at 10,000 magnifications using an electron microscope (SEM), and has a size of 0.1 to 5 mu m, preferably 0.4 to 2.0 mu m . When the average particle diameter is less than 0.1 탆, the light permeability is deteriorated and a pattern having a high precision is hardly drawn. On the other hand, when the average particle diameter exceeds 5 탆, it is difficult to obtain the line edge linearity. Further, it is preferable to use one having an average particle size of 0.5 to 3.5 mu m as measured by a micro-track.
The silver (B-2) preferably has a specific surface area of 0.01 to 2.0 m 2 / g, preferably 0.1 to 1.0 m 2 / g. When the specific surface area is less than 0.01 m < 2 > / g, sedimentation tends to occur during storage, while when the specific surface area exceeds 2.0 m < 2 > / g, oil absorption becomes large and fluidity of the paste is impaired.
The blending ratio of silver (B-2) is preferably 50 to 90 parts by mass relative to 100 parts by mass of the photosensitive composition of the present invention. When the blend ratio of the silver (B-2) is less than the above range, sufficient conductivity of the conductive pattern obtained from such a paste can not be obtained. On the other hand, when the blend ratio exceeds the above range, the adhesion becomes poor .
(iii) Furthermore, when the photosensitive composition of the present invention is used for forming a black color and conductivity in a baked product pattern thereof, specifically, for forming a black layer of a bus electrode, the photosensitive composition of the present invention is prescribed as a conductive black paste (B-1) and silver (B-2) that exhibit black are used as the main component as the inorganic component (B).
As described above, even when the photosensitive composition is formulated by mixing the coloring agent (B-1) and / or the silver powder (B-2) that exhibits black as the main component of the inorganic component (B), the strength of the fired film, It is preferable to add the above glass powder (B-3). The compounding ratio is preferably 1 to 40 parts by mass, more preferably 2 to 20 parts by mass, in the whole composition. 1 part by mass or more is preferable from the viewpoint of improving the adhesiveness with the base material, and if it exceeds 40 parts by mass, the composition may be thickened or gelated, which is not preferable.
(iv) When the photosensitive composition of the present invention is formulated as a glass paste for forming a barrier rib pattern, the glass powder (B-3) is used as the main component as the inorganic component (B).
To the photosensitive composition of the present invention, a boric acid and / or a phosphorus compound described later may be added to improve the storage stability.
Examples of the radically polymerizable unsaturated group-containing compound (C) used in the present invention include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and the like Hydroxyalkyl acrylates; Mono or diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; Acrylamides such as N, N-dimethyl acrylamide, N-methylol acrylamide and N, N-dimethylaminopropylacrylamide; Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; Polyhydric alcohols such as hexanediol, trimethylol propane, pentaerythritol, dipentaerythritol, and tris-hydroxyethylisocyanurate, or polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts thereof; Phenoxy acrylate, bisphenol A diacrylate, and acrylates such as 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; A polyfunctional or monofunctional polyurethane acrylate which is an isocyanate-modified product of the hydroxyalkyl acrylate; And melamine acrylate, and / or each methacrylate corresponding to the above-mentioned acrylate. These may be used alone or in combination of two or more. Among these compounds, compounds having a plurality of radically polymerizable unsaturated groups in one molecule, such as pentaerythritol triacrylate and dipentaerythritol hexaacrylate, are preferable because they are excellent in photo-curability.
Hereinafter, this compound is sometimes referred to as a polymerizable monomer (C).
The compounding ratio of the compound (C) having a radically polymerizable unsaturated group is preferably 5 to 100 parts by mass, more preferably 10 to 70 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (A). When the compounding ratio is less than 5 parts by mass, the photocurability is lowered and pattern formation due to the alkali development after irradiation with active energy rays becomes difficult, which is not preferable. On the other hand, if it exceeds 100 parts by mass, the solubility in an aqueous alkaline solution is lowered or the coating film becomes weak, which is not preferable.
It is important to use a liquid phosphine oxide-based photopolymerization initiator (D-1) as the photopolymerization initiator (D) used in the photosensitive composition of the present invention to solve the problems of the present invention. In other words, it has been found that conventionally used photopolymerization initiators have low solubility in solvents and crystallization of the photopolymerization initiator occurs even when the appearance is uniform as a paste by cooling preservation, which causes a defect in the pattern to be formed , It is possible to obtain a good pattern free from defects such as pinholes and line defects by using a liquid photopolymerization initiator at room temperature. In addition, since a large amount of a solvent which has been used for dissolving a compound having a low solubility is not necessary in the present invention, it is also preferable from the viewpoint of environmental load reduction.
As the liquid phase phosphine oxide-based photopolymerization initiator (D-1), it is particularly preferable to have a structure represented by the following formula (I).
(I)
(Wherein R 1 is a linear or branched alkyl group having 1 to 12 carbon atoms and R 2 is an aryl group substituted with a cyclohexyl group, a cyclopentyl group, an aryl group, a halogen atom, an alkyl group or an alkoxy group, Lt; / RTI > to 20 carbon atoms)
In the present invention, the liquid phase means liquid at room temperature. The room temperature means 10 to 40 占 폚 and the liquid phase at room temperature means that when a test tube is horizontally placed in a test tube having an inner diameter of 30 mm and a height of 55 mm in a temperature range of 10 to 40 占 폚, It is said to be within 90 seconds. As the phosphine oxide-based photopolymerization initiator (D-1) which is liquid at room temperature, ethyl 2,4,6-trimethylbenzoyl phenylphosphinate and the like are preferably used.
In the present invention, the liquid phase phosphine oxide-based photopolymerization initiator (D-1) may contain not only a compound which is liquid at room temperature but also a mixture of a compound which is solid at room temperature and a compound which is liquid, Initiation system. Specifically, it is preferable to use ethyl 2,4,6-trimethylbenzoyl phenylphosphinate which is liquid at room temperature, 2,4,6-trimethylbenzoyldiphenylphosphine oxide or bis (2,4,6-trimethylbenzoyl) phenyl Or a phosphine oxide-based photopolymerization initiator, which is solid at room temperature, such as phosphine oxide, phosphine oxide, and phosphine oxide. The mixing ratio thereof is preferably 70 to 98% by mass of a phosphine oxide-based photopolymerization initiator which is liquid at room temperature, and 2 to 30% by mass of a phosphine oxide-based polymerization initiator which is solid at room temperature.
The mixing ratio of the liquid phase phosphine oxide-based photopolymerization initiator (D-1) is preferably 0.5 to 40 parts by mass, more preferably 1 to 30 parts by mass, Preferably 0.5 to 60 parts by mass, more preferably 1 to 50 parts by mass in the case of non-conductive paste. If the compounding ratio of the phosphine oxide-based photopolymerization initiator (D-1) does not satisfy the above range, it is not preferable because sufficient curability can not be obtained. If the blending ratio exceeds the above range, Resulting in an increase in the cost of the product.
To the photosensitive composition of the present invention, it is preferable to use the oxime-based photopolymerization initiator (D-2) as the photopolymerization initiator (D) in order to further increase the sensitivity. As the oxime-based photopolymerization initiator (D-2), a compound represented by the following formula (IV) may be used.
(IV)
(Wherein 1 or 2 R 1 is represented by formula V, and the other R 1 represents a hydrogen atom, a methyl group, an ethyl group, a phenyl group or a halogen atom)
(V)
(Wherein 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)
Examples of such a compound include 2- (acetyloxyiminomethyl) thioxanthien-9-one represented by the following formula (VI), and CGI-325 manufactured by Ciba Specialty Chemicals Co., Ltd. as a commercial product.
≪ Formula (VI)
In addition to the above compounds, the oxime-based photopolymerization initiator (D-2) may be prepared by reacting 1,2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime)] (manufactured by Ciba Specialty Chemicals, , 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O-acetyloxime) (Ciba Specialty Ltd., trade name: Irgacure OXE02), and the like are also preferably used.
The blending ratio of the oxime-based photopolymerization initiator (D-2) is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the carboxyl-containing resin (A). When the blending ratio of the oxime-based photopolymerization initiator (D-2) is less than 0.05 part by mass, it is not preferable to further increase the sensitivity. On the other hand, if it exceeds 10 parts by mass, the curing property of the thick film is lowered, leading to an increase in the cost of the product, which is not preferable.
The blending ratio of the oxime-based photopolymerization initiator (D-2) is lower than that of the liquid phase phosphine oxide-based photopolymerization initiator (D-1) containing the structure represented by the above formula (I) . D-2] / [D-1] when the compounding ratio of the oxime-based photopolymerization initiator = [D-2] and the compounding rate of the phosphine oxide-based photopolymerization initiator = It is preferably in the range of 1/2 to 1/40 for the conductive paste and 1/2 to 1/60 for the non-conductive paste. When [D-2] / [D-1] exceeds the above range, sufficient deep curing property is hardly obtained due to the influence of the oxime-based photopolymerization initiator (D-2). On the other hand, It is not preferable from the standpoint of deterioration.
The photosensitive composition of the present invention can further contain benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and the like in the range of not causing crystal precipitation by preservation at low temperature as required, Alkyl ethers; 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- Aminoacetophenes such as 1; Anthraquinones such as 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, and 1-chloro anthraquinone; Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone; Or xanthones; (2,6-dimethoxybenzoyl) -2,4,4-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide And a photopolymerization initiator such as phosphine oxides such as a seed may be used in combination. It is particularly preferable to use a thioxanthone photopolymerization initiator such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone or 2,4-diisopropylthioxanthone in combination It is preferable from the viewpoint of deep-part curability.
In addition, boric acid and / or phosphorus compounds are preferably added to the photosensitive composition of the present invention in order to enhance storage stability.
Such boric acid is preferably used in an average particle size (D50) undifferentiated by a jet mill, a ball mill, a roll mill or the like to preferably 20 mu m or less, more preferably 5 mu m or less. Such pulverized particles are desirably used promptly after pulverization because they tend to be hygroscopic and re-aggregated. It may also be pulverized together with resin or solvent contained in the paste.
The blending ratio of such boric acid is suitably 0.01 to 10 parts by mass, preferably 0.1 to 2 parts by mass based on 100 parts by mass of the glass powder (B-3). When the blending ratio of boric acid is less than 0.01 part by mass with respect to 100 parts by mass of the glass powder (B-3), there is no effect of improving the storage stability.
When boric acid is mixed in this way, it is required to use a hydrophobic solvent having a solubility of 20 g or less in 100 g of water at 25 캜. When an organic solvent having high solubility in water is used, water dissolved in the organic solvent ionizes the metal contained in the glass powder (B-3) to cause gelation, which is not preferable.
As the phosphorus compound, phosphorus compounds containing a structure represented by the following formula (II) or (III) are preferably compounded.
≪
(III)
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, isopropyl phosphate, diisopropyl phosphate, , Methyl phosphite, ethyl phosphite, phosphite, butyl phosphite, phenyl phosphite, dimethyl phosphite, diethyl phosphite, dibutyl phosphite, dibutyl phosphite, diphenyl phosphite, diphenyl phosphite, diisopropyl phosphite, diisopropyl phosphite, (2-methacryloyloxyethyl) acid phosphate, mono (2-acryloyloxyethyl) acid phosphate, di (2-methacryloyloxy) ethyl phosphate, Oxyethyl) acid phosphate, di (2-acryloyloxyethyl) acid phosphate, ethyldiethylphosphonoacetate, ethyl acid phosphate, butyl acid phosphate, butyl pyrophosphate 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 may be used alone or in combination of two or more.
The compounding ratio of these phosphorus compounds is preferably 10 parts by mass or less, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the glass powder (B-3). If the compounding ratio of the phosphorus compound exceeds 10 parts by mass based on 100 parts by mass of the glass powder (B-3), the firing property is lowered, which is not preferable.
In the photosensitive composition of the present invention, an organic solvent may be used for the synthesis of the carboxyl group-containing resin (A), preparation of a composition, or viscosity adjustment for application to a substrate or a carrier film. Specific examples thereof include 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 and triethylene glycol monoethyl ether ; Acetic acid 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 ether such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha. These solvents may be used alone or in combination of two or more.
When boric acid is added as described above, it is preferable to use a hydrophobic solvent having a solubility of 20 g or less in 100 g of water at 25 캜.
If necessary, the photosensitive composition of the present invention can further contain a heat polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, pyrogallol, and phenothiazine, a thickener such as fine silica, organic bentonite, montmorillonite, , Defoaming agents such as fluorine-based agents and polymeric agents, and / or leveling agents, and silane coupling agents such as imidazole-based, thiazole-based, and triazole-based agents.
The photosensitive composition of the present invention as described above can be prepared by a method such as dip coating, flow coating, roll coating, bar coating, die coating, screen printing, A coating method, a printing method, a curtain coating method, and the like, and is dried, for example, at about 60 to 120 DEG C for about 5 to 40 minutes to form a tack free coating film. Alternatively, a tack-free coating film can be formed by applying the above composition on a carrier film, drying it, and winding it up as a film on the substrate.
Further, the absorbance per 1 mu m of the film thickness dried in this way is preferably 0.01 to 0.8 in terms of pattern formability. If the absorbance is less than 0.01, the light absorption of the coating film becomes insufficient and image formation becomes difficult, which is not preferable. On the other hand, when the absorbance is more than 0.8, the deep portion curing property is lowered, and the pattern shape tends to become an undercut state, which is not preferable. When the colorant (B-1) exhibiting black is contained as the inorganic component (B), the absorbance is more preferably 0.1 to 0.8, and when the colorant (B-1) It is more preferable that the absorbance is 0.01 to 0.4. (D-1), the oxime-based photopolymerization initiator (D-2), and the inorganic component (B) in order to adjust the range of the absorbance to 0.01 to 0.8 .
Thereafter, the resist film is selectively exposed to an active energy ray through a photomask having a pattern formed thereon by a contact type (or noncontact type), and the unexposed portion is exposed to a dilute alkali aqueous solution (for example, a 0.3 to 3% aqueous solution of sodium carbonate) Thereby forming a pattern.
As an exposure apparatus used for irradiation with the active energy rays, a direct imaging apparatus (for example, a laser direct imaging apparatus that draws an image with a laser directly by CAD data from a computer) can be used. Examples of the active energy ray source include a laser diode, a gas laser, and a solid laser that exhibit laser light having a maximum wavelength in the range of 350 nm to 420 nm, and a laser diode is particularly preferable.
As the direct drawing apparatus, for example, those available from Nippon Orbotex, manufactured by Pentax, manufactured by Hitachi Biomecanics, manufactured by Ball & Semiconductor, etc. may be used, and any device may be used.
Further, a conventional exposure apparatus other than the above-mentioned direct drawing apparatus can be used. Examples of the light source include a halogen lamp, a high-pressure mercury lamp, a laser beam, a metal halide lamp, a black lamp, and an electrodeless lamp.
In addition, a spraying method, a dipping method, or the like is used for the above-mentioned phenomenon. Examples of the developer include aqueous solutions of metal alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium silicate; aqueous amine solutions such as monoethanolamine, diethanolamine, triethanolamine and tetramethylammoniumhydroxide, especially up to about 1.5% Is preferably used. However, the aqueous solution is not limited to the developer as described above, as long as the carboxyl group of the carboxyl group-containing resin (A) in the composition can be saponified to remove the uncured portion (unexposed portion). Further, in order to remove unnecessary developing solution after development, it is preferable to conduct the acid treatment or acid neutralization.
The substrate with the pattern formed by the above-described phenomenon can be sintered at about 400 to 600 DEG C in the air or under an atmosphere of nitrogen to form various desired patterns.
<Examples>
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)
Methyl methacrylate and methacrylic acid were added in a molar ratio of 0.87: 0.13 to a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, and dipropylene glycol monomethyl ether as a solvent and azobisisobutyronitrile as a catalyst , And the mixture was stirred at 80 DEG 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. The measurement of the weight average molecular weight of the obtained copolymer resin was carried out in the same manner as in Example 1 except that a pump LC-6 AD manufactured by Shimadzu Corporation and a column Shodex (registered trademark) KF-804, KF-803, KF manufactured by Showa Denko K.K. -802 were 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)
A flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser was charged with 0.76: 0.24 by mole of methyl methacrylate and methacrylic acid, and dipropylene glycol monomethyl ether as a solvent and azobisisobutyronitrile And the mixture was stirred at 80 ° C for 6 hours in a nitrogen atmosphere to obtain a carboxyl group-containing resin solution. This carboxyl-containing resin solution was cooled, and methylhydroquinone was used as a polymerization inhibitor and tetrabutylphosphonium bromide was used as a catalyst. Glycidyl methacrylate was reacted at 95 to 105 ° C for 16 hours with 1 mole of the carboxyl group of the resin And 0.12 mol, respectively, at an addition molar ratio, and the reaction product was cooled and then taken out. 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. The weight average molecular weight was measured by the same method as the method of measuring the weight average molecular weight in the copolymer resin of the A-1 varnish.
(i) black paste composition
Examples 1 to 8 and Comparative Examples 1 to 2
The blending components shown in Table 1-1 using the A-1 varnish and the A-2 varnish obtained in the above Synthesis Example were kneaded by a three-roll mill to obtain a black paste composition.
<Table 1-1>
(ii) silver paste composition
Examples 9 to 16 and Comparative Examples 3 to 4
The blending components shown in Table 1-2 using the A-1 varnish and the A-2 varnish obtained in the above Synthesis Example were kneaded by a three-roll mill to obtain a silver paste composition.
<Table 1-2>
(iii) black paste is a paste composition
Examples 17 to 24 and Comparative Examples 5 to 6
The blending components shown in Table 1-3 using the A-1 varnish and the A-2 varnish obtained in the above Synthesis Example were kneaded by a three-roll mill to obtain a black silver paste composition.
<Table 1-3>
[1] Various paste compositions of Examples 1 to 24 and Comparative Examples 1 to 6 were applied to the entire surface of a glass substrate using a 300 mesh polyester screen. Subsequently, the film was dried at 90 DEG C for 20 minutes using a hot-air circulation type drying furnace to form a film having favorable dry touch. Subsequently, a resist pattern was formed in a stripe pattern (black paste: line width (L): 100 m, space width (S): 150 m; silver paste: L / S = 50/200 m; Directly and imagewise exposure apparatus (DI-μ10, manufactured by Pentax) having a blue-violet laser having a center wavelength of 405 nm as a light source was used as the light source, and the accumulated light quantity on the composition was 40 mJ / Cm < 2 > for black and 100 mJ / cm < 2 > for paste. Thereafter, development was performed for 20 seconds using a 0.4 mass% Na 2 CO 3 aqueous solution having a liquid temperature of 30 캜, and the plate was washed with water. Finally, the furnace was fired in air using an electric furnace.
The firing was carried out by raising the temperature from room temperature to 590 캜 at a heating rate of 5 캜 / minute, holding the same for 10 minutes, and then cooling to room temperature.
Evaluation results of the various characteristics of each substrate 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
The obtained various paste compositions were stored in a freezer at -20 占 폚 for 7 days, coated on a glass substrate and dried to visually observe the state of the surface to evaluate whether or not foreign substances resulted from crystal precipitation of the photopolymerization initiator.
&Amp; cir &: A smooth coating film was formed, and no foreign substance due to crystallization of the initiator was observed
DELTA: Foreign substance due to crystallization of the initiator exists in a part of the coating film
X: Existence of foreign substances due to crystallization of the initiator on the entire coating film
(2) Measurement of absorbance
The absorbance of an evaluation substrate on which soda lime glass was formed with a dry film thickness of 5 mu m and 10 mu m was measured using an ultraviolet visible spectrophotometer. From the obtained data, the absorbance per 1 mu m of thickness at 405 nm was calculated.
(3) Evaluation of laser photosensitivity
(Black paste: L / S = 100/150 占 퐉; silver paste: L / S = 50/200 占 퐉; mJ / ㎠, black is then exposed to a 100 mJ / ㎠ the paste, subjected to 20 seconds development using a 0.4 mass% Na 2 CO 3 aqueous solution of a liquid temperature of 30 ℃, was evaluated in a line formation whether the light microscope.
The evaluation criteria are as follows.
○: No defect was observed at all.
?: Some defects were observed.
X: Line can not be formed.
(4) Calculation of minimum exposure dose
(Black paste: L / S = 100/150 占 퐉, silver paste: L / S = 50/200 占 퐉 or black paste: L / S = 50/200 占 퐉) was performed by changing the accumulated light quantity The minimum amount of exposure that can be formed without defect is measured. In addition, since the comparative example is not practical since the exposure time with the laser is long, no further tests have been conducted. In Comparative Example 5, image formation with laser light having a central wavelength of 405 nm could not be performed.
(5) Line shape after pattern formation
A pattern after development in various paste compositions of alkali developing type in the case of exposure at the minimum exposure amount was observed with a microscope to evaluate whether irregular fluctuation or tangling in the line occurred. The evaluation criteria are as follows.
○: No irregular fluctuation, no tangling.
?: Slight irregular fluctuation and tangling.
X: Irregular fluctuations and tangles are present.
(6) Line shape after firing
The pattern of the line after firing was observed by a microscope to see whether the line was irregularly fluctuated or tangled. The evaluation criteria are as follows.
○: No irregular fluctuation, no tangling.
?: Slight irregular fluctuation and tangling.
X: Irregular fluctuations and tangles are present.
(7) Adhesion
The adhesiveness was evaluated by peeling with a cellophane adhesive tape to evaluate the presence or absence of pattern peeling. The evaluation criteria are as follows.
○: No peeling of the pattern.
△: There is some pattern peeling.
X: There is a lot of pattern peeling.
(8) Measurement of resistivity value
The resistivity values of silver paste compositions (Examples 9 to 16, Comparative Examples 3 to 4) and black silver paste compositions (Examples 17 to 24 and Comparative Examples 5 to 6) were measured.
A test substrate was prepared in the same manner as in the evaluation of the above (line shape after firing), except that the exposure was performed using CAD data having a pattern dimension of 0.4 cm x 10 cm. The resistance value of the fired film was measured on the thus-obtained test substrate using a Milli-Oh Hi 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.
<Table 2-1>
<Table 2-2>
<Table 2-3>
As is apparent from the results shown in Tables 2-1 to 2-3, the black paste composition, silver paste composition and black silver paste composition of the present invention all exhibited excellent storage stability without causing crystal precipitation due to low-temperature storage .
<Table 3-1>
<Table 3-2>
<Table 3-3>
As is evident from the results shown in Tables 3-1 to 3-3, it was found that the various paste compositions of the present invention had a sufficient sensitivity to laser light and could form a pattern of fixed lines. Further, when used in combination with the oxime-based photopolymerization initiator (D-2), it was found that the sensitivity was further improved and thus it was more useful for laser exposure. In addition, the various paste compositions of the present invention had no irregular fluctuation in the line shape after firing, and were also excellent in adhesion to a substrate. In addition, the black paste composition of the present invention could satisfy the blackness after firing, and the silver paste composition and the black silver paste composition of the present invention were sufficient as an electrode material for the specific resistance value.
[2] Then, pattern formation was also performed in a lamp-type exposure. Using the various paste compositions of Examples 1 to 24 and Comparative Examples 1 to 6, the entire surface of the glass substrate was coated with a 300 mesh polyester screen. Subsequently, the film was dried at 90 DEG C for 20 minutes using a hot-air circulation type drying furnace to form a film having favorable dry touch. Subsequently, a glass plate having a negative pattern of a stripe pattern (black paste: L / S = 100/150 mu m; silver paste: L / S = 50/200 mu m; black paste: L / S = 50/200 mu m) (MAT-5301 manufactured by Hakuto Co., Ltd.) equipped with an ultra-high pressure mercury lamp as a light source as a photomask, 50 mJ / cm 2 for a black paste and a silver paste, and 100 mJ / mJ / cm < 2 >. Thereafter, development was carried out for 20 seconds using a 0.4 mass% Na 2 CO 3 aqueous solution at a liquid temperature of 30 캜, and the plate was washed with water. Finally, the furnace was fired in air using an electric furnace.
The firing was carried out by raising the temperature from room temperature to 590 캜 at a temperature raising rate of 5 캜 / minute, holding it for 10 minutes, and then cooling to room temperature.
The evaluation results of 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) Evaluation of photosensitivity in lamp-type exposure
(Black paste: L / S = 100/150 占 퐉; silver paste: L / S = 50/200 占 퐉; mJ / cm < 2 > for black, and 100 mJ / cm < 2 > for paste, and developed for 20 seconds using a 0.4 mass% Na 2 CO 3 aqueous solution at a liquid temperature of 30 ° C to evaluate the formation of lines by an optical microscope. The evaluation criteria are as follows.
○: No defect was observed at all.
?: Some defects were observed.
X: Line can not be formed.
(10) Calculation of minimum exposure dose
(Black paste: L / S = 100/150 占 퐉, silver paste: L / S = 50/200 占 퐉 or black paste: L / S = 50/200 占 퐉) was performed by changing the accumulated light quantity The minimum amount of exposure that can be formed without defect is measured.
(11) Line shape after pattern formation
A pattern after development in various paste compositions of alkali developing type in the case of exposure at the minimum exposure amount was observed with a microscope to evaluate whether irregular fluctuation or tangling in the line occurred. The evaluation criteria are as follows.
○: No irregular fluctuation, no tangling.
?: Slight irregular fluctuation and tangling.
X: Irregular fluctuations and tangles are present.
(12) Line shape after firing
The pattern of the line after firing was observed by a microscope to see whether the line was irregularly fluctuated or tangled. The evaluation criteria are as follows.
○: No irregular fluctuation, no tangling.
?: Slight irregular fluctuation and tangling.
X: Irregular fluctuations and tangles are present.
(13) Adhesion
The adhesiveness was evaluated by peeling with a cellophane adhesive tape to judge whether or not the pattern was peeled off. The evaluation criteria are as follows.
○: No peeling of the pattern.
△: There is some pattern peeling.
X: There is a lot of pattern peeling.
(14) Measurement of resistivity value
The resistivity values of silver paste compositions (Examples 9 to 16, Comparative Examples 3 to 4) and black silver paste compositions (Examples 17 to 24 and Comparative Examples 5 to 6) were measured.
A test substrate was prepared in the same manner as in the evaluation of the above (line shape after firing), except that the exposure was performed using CAD data having a pattern dimension of 0.4 cm x 10 cm. The resistance value of the fired film was measured on the thus-obtained test substrate using a Milli-Oh Hi 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.
<Table 4-1>
<Table 4-2>
<Table 4-3>
As apparent from the results shown in Tables 4-1 to 4-3, the various alkaline developing paste compositions of the present invention have sufficient sensitivity even when an ultrahigh-pressure mercury lamp (lamp-type exposure) is used as a light source, It is possible to form a pattern. In addition, since it has succeeded in dramatically increasing the sensitivity, it is possible to achieve a remarkable decrease in exposure time when applied to conventional lamp-type exposure. In addition, there was no irregular fluctuation in the line shape after firing, good adhesion to the substrate, and excellent storage stability. In addition, the black paste composition of the present invention was satisfactory in blackness after firing regardless of the exposure method, and the silver paste composition and the black silver paste composition of the present invention were sufficient as the electrode material as the specific resistivity.
Claims (8)
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| JP2008040492A JP5210657B2 (en) | 2007-07-18 | 2008-02-21 | Pattern comprising photosensitive composition and fired product thereof |
| JPJP-P-2008-00040492 | 2008-02-21 |
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| KR101138795B1 (en) * | 2008-12-23 | 2012-04-24 | 제일모직주식회사 | Photosensitive composition and plasma display electrode fabricated using the same |
| JP5377021B2 (en) * | 2009-03-23 | 2013-12-25 | 太陽ホールディングス株式会社 | Curable resin composition, dry film and printed wiring board using the same |
| JP5377020B2 (en) * | 2009-03-23 | 2013-12-25 | 太陽ホールディングス株式会社 | Photo-curable thermosetting resin composition, dry film and cured product thereof, and printed wiring board using them |
| JP5349113B2 (en) * | 2009-03-30 | 2013-11-20 | 太陽ホールディングス株式会社 | Photosensitive resin composition, dry film and printed wiring board using the same |
| KR20110014798A (en) * | 2009-08-06 | 2011-02-14 | 주식회사 동진쎄미켐 | Photosensitive paste for elextrode of plasma display pannel |
| JP5732222B2 (en) * | 2010-09-30 | 2015-06-10 | 太陽ホールディングス株式会社 | Photosensitive resin composition |
| JP2012194522A (en) * | 2011-03-01 | 2012-10-11 | Dainippon Printing Co Ltd | Contrast-improving filter and image display device using filter |
| EP2700679A4 (en) * | 2011-04-20 | 2015-01-07 | Adeka Corp | Novel compound having alpha-cyanoacrylate structure, dye, and coloring photosensitive composition |
| JP6758070B2 (en) * | 2016-03-31 | 2020-09-23 | 日鉄ケミカル＆マテリアル株式会社 | A method for manufacturing a photosensitive resin composition for a light-shielding film, a display substrate provided with a light-shielding film obtained by curing the photosensitive resin composition, and a display substrate. |
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| JP2000066386A (en) | 1998-08-21 | 2000-03-03 | Jsr Corp | Dry film resist and its production |
| WO2007007800A1 (en) * | 2005-07-13 | 2007-01-18 | Taiyo Ink Mfg. Co., Ltd. | Black paste composition, method for black matrix pattern formation using the same, and its black matrix pattern |
| WO2007007802A1 (en) * | 2005-07-13 | 2007-01-18 | Taiyo Ink Mfg. Co., Ltd. | Silver paste composition, method for electrically conductive pattern formation using the same, and its electrically conductive pattern |
| JP2007248846A (en) | 2006-03-16 | 2007-09-27 | Fujifilm Corp | Photosensitive composition, film, and laminate, and permanent pattern forming method, permanent pattern, and printed circuit board |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002172867A (en) * | 2000-12-08 | 2002-06-18 | Fuji Photo Film Co Ltd | Lithographic printing original plate |
| JP2002182377A (en) * | 2000-12-13 | 2002-06-26 | Fuji Photo Film Co Ltd | Visible rays polymerizable composition, photosensitive and heat sensitive recording material and image recording method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000066386A (en) | 1998-08-21 | 2000-03-03 | Jsr Corp | Dry film resist and its production |
| WO2007007800A1 (en) * | 2005-07-13 | 2007-01-18 | Taiyo Ink Mfg. Co., Ltd. | Black paste composition, method for black matrix pattern formation using the same, and its black matrix pattern |
| WO2007007802A1 (en) * | 2005-07-13 | 2007-01-18 | Taiyo Ink Mfg. Co., Ltd. | Silver paste composition, method for electrically conductive pattern formation using the same, and its electrically conductive pattern |
| JP2007248846A (en) | 2006-03-16 | 2007-09-27 | Fujifilm Corp | Photosensitive composition, film, and laminate, and permanent pattern forming method, permanent pattern, and printed circuit board |
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| JP2009042732A (en) | 2009-02-26 |
| KR20090009092A (en) | 2009-01-22 |
| JP5210657B2 (en) | 2013-06-12 |
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