JP5183160B2 - Black paste composition, method for forming black matrix pattern using the same, and black matrix pattern - Google Patents
Black paste composition, method for forming black matrix pattern using the same, and black matrix pattern Download PDFInfo
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- JP5183160B2 JP5183160B2 JP2007297033A JP2007297033A JP5183160B2 JP 5183160 B2 JP5183160 B2 JP 5183160B2 JP 2007297033 A JP2007297033 A JP 2007297033A JP 2007297033 A JP2007297033 A JP 2007297033A JP 5183160 B2 JP5183160 B2 JP 5183160B2
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- black matrix
- matrix pattern
- black
- pattern
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- 239000000203 mixture Substances 0.000 title claims description 68
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- 238000000034 method Methods 0.000 title claims description 28
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- 239000011347 resin Substances 0.000 claims description 48
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 44
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- 239000003999 initiator Substances 0.000 claims description 25
- 238000011161 development Methods 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 22
- 239000003513 alkali Substances 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 21
- 238000010304 firing Methods 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 18
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- 239000000049 pigment Substances 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
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- 238000001035 drying Methods 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 238000002835 absorbance Methods 0.000 claims description 5
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- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
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- 239000010452 phosphate Substances 0.000 description 9
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
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- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 4
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- 229920006395 saturated elastomer Polymers 0.000 description 4
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- VMKBJESZDNXQHG-UHFFFAOYSA-N [(9-oxothioxanthen-2-yl)methylideneamino] acetate Chemical compound C1=CC=C2C(=O)C3=CC(C=NOC(=O)C)=CC=C3SC2=C1 VMKBJESZDNXQHG-UHFFFAOYSA-N 0.000 description 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229960002130 benzoin Drugs 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000007607 die coating method Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
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- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
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- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- GIMQKKFOOYOQGB-UHFFFAOYSA-N 2,2-diethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)(OCC)C(=O)C1=CC=CC=C1 GIMQKKFOOYOQGB-UHFFFAOYSA-N 0.000 description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 2
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- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 2
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- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 2
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- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 2
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- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- NFORZJQPTUSMRL-UHFFFAOYSA-N dipropan-2-yl hydrogen phosphite Chemical compound CC(C)OP(O)OC(C)C NFORZJQPTUSMRL-UHFFFAOYSA-N 0.000 description 2
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- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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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
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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
- 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
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
Description
本発明は、各種ブラックマトリックスの形成に適した黒色ペースト組成物、及びそれを用いたブラックマトリックスパターンの形成方法、並びにそのブラックマトリックスパターンに関する。さらに詳しくは、最大波長が３５０ｎｍ〜４２０ｎｍのレーザー発振光源を用いたレーザー・ダイレクト・イメージング装置に適し、精細なブラックマトリックスパターンを効率良く形成するのに有用で、かつ保存安定性に優れた黒色ペースト組成物、及びそれを用いたブラックマトリックスパターンの形成方法、並びにそのブラックマトリックスパターンに関する。 The present invention relates to a black paste composition suitable for forming various black matrices, a method for forming a black matrix pattern using the same, and the black matrix pattern. More specifically, a black paste suitable for a laser direct imaging apparatus using a laser oscillation light source having a maximum wavelength of 350 nm to 420 nm, useful for efficiently forming a fine black matrix pattern, and having excellent storage stability. The present invention relates to a composition, a method for forming a black matrix pattern using the composition, and the black matrix pattern.
従来、薄型ディスプレイの前面板には、ブラックマトリックスパターンが使用されている。そしてその形成法は、例えばガラス基板上に、ブラックマトリックスパターン用のレジストを塗布乾燥して塗膜とし、該塗膜を回路や電極パターンが描かれたフォトマスクを通して画像を露光した後、露光部と非露光部の現像液に対する溶解性の差を利用してアルカリ水溶液で現像処理することによって回路や電極パターンに対応したレジスト層を形成し焼成することによってガラス基板に密着したブラックマトリックスパターンを形成していた。 Conventionally, a black matrix pattern is used for a front plate of a thin display. And the formation method is, for example, applying a black matrix pattern resist on a glass substrate and drying to form a coating film, exposing the image through a photomask on which the circuit and electrode patterns are drawn, and then exposing the exposed portion. The resist layer corresponding to the circuit and electrode pattern is formed by developing with an alkaline aqueous solution using the difference in solubility in the developer in the unexposed area and the unexposed area, and a black matrix pattern that adheres to the glass substrate is formed by baking. Was.
しかしながら、これらのパターン露光工法では、フォトマスクに欠損がまったくないわけではなく、形成したパターンにも欠損が生じて、フォトマスクおよびガラス基板の伸縮により位置ずれが生じる場合がある。特に細線のパターン露光が難しく、大型のパネルの生産の不良率低減が困難であった。また、フォトマスク作成に時間・コストを要することから、特に少量多品種の生産や試作等の場合、フォトマスクのコストが増大することが問題視されていた。 However, in these pattern exposure methods, the photomask is not completely free of defects, and the formed pattern may be defective, and displacement may occur due to expansion and contraction of the photomask and the glass substrate. In particular, it was difficult to expose fine lines, and it was difficult to reduce the defective rate in the production of large panels. Moreover, since time and cost are required for photomask preparation, it has been regarded as a problem that the cost of the photomask increases, particularly in the case of production of a small quantity of various products or trial production.
このようなことから、ＣＡＤ（Computer Aided Design）で作成した回路を、レーザー光により直接描画するレーザー・ダイレクト・イメージング工法（Laser Direct Imaging、以下ＬＤＩという）が見直されてきている。ＬＤＩは、ＣＡＤデータから直接パターンの描画を行うため、少量多品種の生産が効率的に行える他、フォトマスクを使わないため位置あわせが正確で、スケーリングの補正も容易であり、フォトマスクへの異物の付着、汚れ、傷の管理の必要がなくなる等、多くの利点を有する。 For these reasons, a laser direct imaging method (hereinafter referred to as LDI) in which a circuit created by CAD (Computer Aided Design) is directly drawn by laser light has been reviewed. Since LDI draws patterns directly from CAD data, it can efficiently produce a small quantity and a wide variety of products, and since it does not use a photomask, alignment is accurate and scaling correction is easy. There are many advantages such as eliminating the need for foreign matter adhesion, dirt, and scratch management.
しかし、ＬＤＩでは、レーザー走査により直接描画を行うため、フォトマスクを利用して一括で露光する場合に比べて、タクトタイムが長く、スループットの点が不十分であるという欠点を有していた。スループットを改善するには、レーザーの走査速度を上げることが必要であるが、従来の感光性黒色ペースト組成物は、感度が不十分であるため（適正露光量＝３００〜５００ｍＪ／ｃｍ２）、走査速度を上げることが難しいという問題があった。 However, since LDI directly draws by laser scanning, it has the disadvantage that the tact time is long and the throughput is insufficient as compared with the case where exposure is performed all at once using a photomask. In order to improve the throughput, it is necessary to increase the scanning speed of the laser, but since the conventional photosensitive black paste composition has insufficient sensitivity (appropriate exposure = 300 to 500 mJ / cm 2 ), There was a problem that it was difficult to increase the scanning speed.
一方、レーザー走査により感光させる組成物としては、特定の色素増感剤、及びチタノセン化合物等を含有する組成物（例えば、特許文献１、及び特許文献２参照）や、特定のビスアシルフォスフィンオキサイドを含有するレーザー感光性組成物（例えば、特許文献３参照）が提案されているが、充分な感光スピードが得られていなかった。
本発明は、上記問題点に鑑み開発されたものであり、その主たる目的は、最大波長が３５０ｎｍ〜４２０ｎｍのレーザー発振光源を用いたレーザー・ダイレクト・イメージング装置に適し、精細なブラックマトリックスパターンを効率良く形成するのに有用で、かつ保存安定性に優れた黒色ペースト組成物を提供することにある。 また、本発明は、光源として超高圧水銀灯などを用いたランプ式露光でも十分な感度を有し、高精細なパターンを形成できる黒色ペースト組成物を提供することにある。 更に、この黒色ペースト組成物を用いたブラックマトリックスパターンの形成方法、並びにそのブラックマトリックスパターンを提供することにある。 The present invention has been developed in view of the above problems, and its main purpose is to be suitable for a laser direct imaging apparatus using a laser oscillation light source having a maximum wavelength of 350 nm to 420 nm, and to efficiently produce a fine black matrix pattern. An object of the present invention is to provide a black paste composition useful for forming well and having excellent storage stability. Another object of the present invention is to provide a black paste composition that has sufficient sensitivity even in lamp-type exposure using an ultra-high pressure mercury lamp as a light source and can form a high-definition pattern. Furthermore, it is providing the formation method of the black matrix pattern using this black paste composition, and the black matrix pattern.
上記課題を解決するために本発明は以下の構成を備える。 In order to solve the above problems, the present invention comprises the following arrangement.
（式中、ｎは、０〜２の整数を表し、ｍは、１〜３の整数を表し、ｎ＋ｍ＝３となる関係にある。また、Ｒ１、Ｒ２は、炭素数１〜２４のアルキル基又はアルコキシ基を表し、Ｒ３は、炭素数１〜６のアルキル基を表す。）
（１）（Ａ）カルボキシル基含有樹脂、（Ｂ）ガラスフリット、（Ｃ）黒色顔料、（Ｄ）一分子内に少なくとも一つ以上のラジカル重合性不飽和基を有する化合物、（Ｅ−１）下記一般式（II）で表わされる官能基を有するオキシムエステル系光重合開始剤、及び（Ｆ）下記一般式（Ｉ）で表わされるアルミニウム化合物を含有することを特徴とするアルカリ現像型の焼成用黒色ペースト組成物。
(In the formula, n represents an integer of 0 to 2, m represents an integer of 1 to 3, and n + m = 3, and R 1 and R 2 have 1 to 24 carbon atoms. Represents an alkyl group or an alkoxy group, and R 3 represents an alkyl group having 1 to 6 carbon atoms.)
(1) (A) carboxyl group-containing resin, (B) glass frit, (C) black pigment, (D) compound having at least one radical polymerizable unsaturated group in one molecule, (E-1) An alkali development type firing composition comprising: an oxime ester photopolymerization initiator having a functional group represented by the following general formula (II); and (F) an aluminum compound represented by the following general formula (I): Black paste composition.
（式中、Ｒ４は、水素原子、炭素数１〜６のアルキル基、又はフェニル基を表わし、Ｒ５は、水素原子、炭素数１〜６のアルキル基を表す。） (In the formula, R 4 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R 5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
（式中、ｎは、０〜２の整数を表し、ｍは、１〜３の整数を表し、ｎ＋ｍ＝３となる関係にある。また、Ｒ１、Ｒ２は、炭素数１〜２４のアルキル基又はアルコキシ基を表し、Ｒ３は、炭素数１〜６のアルキル基を表す。）
（２）前記オキシムエステル系光重合開始剤（Ｅ−１）が、下記一般式（III）で表わされるオキシムエステル系光重合開始剤であることを特徴とする（１）に記載のアルカリ現像型の焼成用黒色ペースト組成物。
(In the formula, n represents an integer of 0 to 2, m represents an integer of 1 to 3, and n + m = 3, and R 1 and R 2 have 1 to 24 carbon atoms. Represents an alkyl group or an alkoxy group, and R 3 represents an alkyl group having 1 to 6 carbon atoms.)
(2) The alkali development type according to (1) , wherein the oxime ester photopolymerization initiator (E-1) is an oxime ester photopolymerization initiator represented by the following general formula (III): A black paste composition for firing .
（式中、１つ又は２つのＲ６は、下記一般式（II）で表わされ（但し、２つのＲ６の場合、Ｒ６が異なる場合を含む）、残りのＲ６は、水素原子、メチル基、フェニル基またはハロゲン原子を表す（但し、Ｒ６がそれぞれ異なる場合を含む）。） (In the formula, one or two R 6 are represented by the following general formula (II) (in the case of two R 6 , including the case where R 6 is different), and the remaining R 6 is a hydrogen atom: , Represents a methyl group, a phenyl group or a halogen atom (provided that R 6 is different from each other).
（式中、Ｒ４は、水素原子、炭素数１〜６のアルキル基、又はフェニル基を表わし、Ｒ５は、水素原子、炭素数１〜６のアルキル基を表す。）
（３）前記カルボキシル基含有樹脂（Ａ）が、（Ａ−１）一つ以上のラジカル重合性不飽和基を有するカルボキシル基含有樹脂であることを特徴とする（１）〜（２）のいずれかに記載のアルカリ現像型の焼成用黒色ペースト組成物。
(In the formula, R 4 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R 5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
(3) Any of (1) to (2) , wherein the carboxyl group-containing resin (A) is (A-1) a carboxyl group-containing resin having one or more radically polymerizable unsaturated groups. An alkali development type black paste composition for baking according to claim 1.
（４）さらに、（Ｅ−２）下記一般式（IV）で表わされる構造を含むフォスフィンオキサイド系光重合開始剤を含有することを特徴とする（１）〜（３）のいずれかに記載のアルカリ現像型の焼成用黒色ペースト組成物。 (4) Further described in any one of (1) to (3) , further comprising (E-2) a phosphine oxide photopolymerization initiator including a structure represented by the following general formula (IV): An alkali development type black paste composition for baking .
（式中、Ｒ７、Ｒ８は、それぞれ独立に、炭素数１〜１０の直鎖状又は分岐状のアルキル基、シクロヘキシル基、シクロペンチル基、アリール基、又はハロゲン原子、アルキル基もしくはアルコキシ基で置換されたアリール基、又はいずれか一方が炭素数１〜２０のカルボニル基を表わす。）
（５）前記（４）に記載の組成物において、前記一般式（II）で表わされる官能基を有するオキシムエステル系光重合開始剤（Ｅ−１）の配合量が、前記一般式（IＶ）で表わされるフォスフィンオキサイド系光重合開始剤（Ｅ−２）の配合量より少ないことを特徴とするアルカリ現像型の焼成用黒色ペースト組成物。
(Wherein R 7 and R 8 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or a halogen atom, an alkyl group or an alkoxy group. A substituted aryl group, or either one represents a carbonyl group having 1 to 20 carbon atoms.)
(5) In the composition according to the above (4) , the amount of the oxime ester photopolymerization initiator (E-1) having the functional group represented by the general formula (II) is the general formula (IV). An alkali developing type black paste composition for baking, which is less than the blending amount of the phosphine oxide photopolymerization initiator (E-2) represented by the formula (1).
（６）前記（１）〜（５）のいずれかに記載の組成物を、塗布乾燥した塗膜は、その膜厚１μｍ当りの吸光度が、０．１〜０．８であることを特徴とするアルカリ現像型の焼成用黒色ペースト組成物。 (6) The coating film obtained by coating and drying the composition according to any one of (1) to (5) above has an absorbance per 1 μm thickness of 0.1 to 0.8. An alkali developing type black paste composition for baking .
（７）前記（１）〜（６）のいずれかに記載の組成物を用いたブラックマトリックスパターンの形成方法であって、
（ｉ）活性エネルギー線を用い、パターン露光する工程と、
（ii）希アルカリ水溶液で現像することにより選択的にパターン形成する工程と、
（iii）４００〜６００℃で焼成させる工程と、
を含むことを特徴とするブラックマトリックスパターンの形成方法。
(7) A method of forming a black matrix pattern using the composition according to any one of (1) to (6) ,
(I) a step of pattern exposure using active energy rays;
(Ii) a step of selectively forming a pattern by developing with a dilute alkaline aqueous solution;
(Iii) a step of baking at 400 to 600 ° C .;
A method for forming a black matrix pattern, comprising:
（８）前記（１）〜（６）のいずれかに記載の組成物を用いたブラックマトリックスパターンの形成方法であって、
（ｉ）最大波長が３５０ｎｍ〜４２０ｎｍのレーザー発振光源を用い、パターン描画する工程と、
（ii）希アルカリ水溶液で現像することにより選択的にパターン形成する工程と、
（iii）４００〜６００℃で焼成させる工程と、
を含むことを特徴とするブラックマトリックスパターンの形成方法。
(8) A method for forming a black matrix pattern using the composition according to any one of (1) to (6) ,
(I) a step of drawing a pattern using a laser oscillation light source having a maximum wavelength of 350 nm to 420 nm;
(Ii) a step of selectively forming a pattern by developing with a dilute alkaline aqueous solution;
(Iii) a step of baking at 400 to 600 ° C .;
A method for forming a black matrix pattern, comprising:
（９）前記（７）に記載のブラックマトリックスパターンの形成方法により得られたブラックマトリックスパターン。 (9) A black matrix pattern obtained by the method for forming a black matrix pattern according to (7) .
（１０）前記（８）に記載のブラックマトリックスパターンの形成方法により得られたブラックマトリックスパターン。 (10) A black matrix pattern obtained by the method for forming a black matrix pattern according to (8) .
（１１）前記（９）又は（１０）に記載のブラックマトリックスパターンを含むプラズマディスプレイパネル。 (11) A plasma display panel comprising the black matrix pattern according to (9) or (10) .
本発明の黒色ペースト組成物によれば、アルミニウム化合物を配合することにより、分散安定性に優れた低粘度の黒色ペーストが得られることからダイコートなどの低粘度液体を用いる塗布方法に対応することも可能である。更には、焼成後のライン形状に不規則なバラツキがなく、基材との密着性にも優れるものとなる。また、本発明の黒色ペースト組成物はオキシムエステル系光重合開始剤を用いることにより活性エネルギー線に対する優れた感度を有し、高精細なパターンを形成することができる。特にオキシムエステル系光重合開始剤を配合する場合、最大波長が３５０ｎｍ〜４２０ｎｍのレーザー発振光源に対して、優れた光硬化性を示すことから、露光装置として、レーザー・ダイレクト・イメージング装置を用いることができ、従来の露光方法で生じていたフォトマスクおよびガラス基板の伸縮により位置ずれが無く、さらにフォトマスクに付着する異物によるパターン欠損が無くなり、信頼性の高いブラックマトリックスパターンを形成することが可能となる。 According to the black paste composition of the present invention, a low-viscosity black paste excellent in dispersion stability can be obtained by blending an aluminum compound, so that it can be applied to a coating method using a low-viscosity liquid such as a die coat. Is possible. Furthermore, there is no irregular variation in the line shape after firing, and the adhesiveness to the substrate is excellent. Moreover, the black paste composition of this invention has the outstanding sensitivity with respect to an active energy ray by using an oxime ester type photoinitiator, and can form a high-definition pattern. In particular, when an oxime ester photopolymerization initiator is blended, a laser direct imaging apparatus is used as an exposure apparatus because it exhibits excellent photocurability for a laser oscillation light source having a maximum wavelength of 350 nm to 420 nm. It is possible to form a highly reliable black matrix pattern because there is no misalignment due to the expansion and contraction of the photomask and glass substrate caused by the conventional exposure method, and there is no pattern loss due to foreign matter adhering to the photomask. It becomes.
また、レーザー・ダイレクト・イメージング装置を用いることにより、フォトマスクが不要になり、また設計から製造への移管が容易になり、さらに不良率の低減により、製品コスト低減が可能となる。 In addition, the use of a laser direct imaging apparatus eliminates the need for a photomask, facilitates the transfer from design to manufacturing, and further reduces the product cost by reducing the defect rate.
以下本発明のアルカリ現像型の黒色ペースト組成物を詳細に説明する。 Hereinafter, the alkali developing type black paste composition of the present invention will be described in detail.
（Ａ）カルボキシル基含有樹脂
本発明の黒色ペースト組成物に含まれるカルボキシル基含有樹脂（Ａ）としては、分子中にカルボキシル基を含有している公知慣用の樹脂化合物が使用できる。
具体的には、下記に列挙するような樹脂が挙げられる。
（１）（メタ）アクリル酸などの不飽和カルボン酸と、それ以外の不飽和二重結合を有する化合物の１種類以上と共重合することにより得られるカルボキシル基含有樹脂、
（２）（メタ）アクリル酸などの不飽和カルボン酸と、それ以外の不飽和二重結合を有する化合物の１種類以上との共重合体に、グリシジル（メタ）アクリレートや３，４−エポキシシクロヘキシルメチル（メタ）アクリレートなどのエポキシ基と不飽和二重結合を有する化合物や（メタ）アクリル酸クロライドなどによって、エチレン性不飽和基をペンダントとして付加させることによって得られるカルボキシル基含有感光性樹脂、
（３）グリシジル（メタ）アクリレートや３，４−エポキシシクロヘキシルメチル（メタ）アクリレート等のエポキシ基と不飽和二重結合を有する化合物と、それ以外の不飽和二重結合を有する化合物との共重合体に、（メタ）アクリル酸などの不飽和カルボン酸を反応させ、生成した二級の水酸基に多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂、
（４）無水マレイン酸などの不飽和二重結合を有する酸無水物と、それ以外の不飽和二重結合を有する化合物との共重合体に、２−ヒドロキシエチル（メタ）アクリレートなどの水酸基と不飽和二重結合を有する化合物を反応させて得られるカルボキシル基含有感光性樹脂、
（５）多官能エポキシ化合物と不飽和モノカルボン酸を反応させ、生成した水酸基に飽和又は不飽和多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂、
（６）ポリビニルアルコール誘導体などの水酸基含有ポリマーに、飽和又は不飽和多塩基酸無水物を反応させた後、生成したカルボン酸に一分子中にエポキシ基と不飽和二重結合を有する化合物を反応させて得られる水酸基及びカルボキシル基含有感光性樹脂、
（７）多官能エポキシ化合物と、不飽和モノカルボン酸と、一分子中に少なくとも１個のアルコール性水酸基と、エポキシ基と反応するアルコール性水酸基以外の１個の反応性基を有する化合物との反応生成物に、飽和又は不飽和多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂、
（８）一分子中に少なくとも２個のオキセタン環を有する多官能オキセタン化合物に不飽和モノカルボン酸を反応させ、得られた変性オキセタン樹脂中の第一級水酸基に対して飽和又は不飽和多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂、及び
（９）多官能エポキシ樹脂に不飽和モノカルボン酸を反応させた後、多塩基酸無水物を反応させて得られるカルボキシル基含有樹脂に、更に、分子中に１個のオキシラン環と１個以上のエチレン性不飽和基を有する化合物を反応させて得られるカルボキシル基含有感光性樹脂などが挙げられるが、これらに限定されるものでは無い。
(A) Carboxyl group-containing resin As the carboxyl group-containing resin (A) contained in the black paste composition of the present invention, a known and commonly used resin compound containing a carboxyl group in the molecule can be used.
Specific examples include the resins listed below.
(1) a carboxyl group-containing resin obtained by copolymerizing with an unsaturated carboxylic acid such as (meth) acrylic acid and one or more other compounds having an unsaturated double bond;
(2) Glycidyl (meth) acrylate or 3,4-epoxycyclohexyl is a copolymer of an unsaturated carboxylic acid such as (meth) acrylic acid and one or more other compounds having an unsaturated double bond. A carboxyl group-containing photosensitive resin obtained by adding an ethylenically unsaturated group as a pendant by a compound having an epoxy group and an unsaturated double bond, such as methyl (meth) acrylate, or (meth) acrylic acid chloride,
(3) Copolymerization of a compound having an unsaturated double bond with an epoxy group such as glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acrylate, and a compound having an unsaturated double bond other than that A carboxyl group-containing photosensitive resin obtained by reacting an unsaturated carboxylic acid such as (meth) acrylic acid with the coalescence and reacting a polybasic acid anhydride with the generated secondary hydroxyl group,
(4) To a copolymer of an acid anhydride having an unsaturated double bond such as maleic anhydride and a compound having an unsaturated double bond other than that, a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; A carboxyl group-containing photosensitive resin obtained by reacting a compound having an unsaturated double bond,
(5) a carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting the generated hydroxyl group with a saturated or unsaturated polybasic acid anhydride,
(6) After reacting a 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 polyfunctional epoxy compound, an unsaturated monocarboxylic acid, at least one alcoholic hydroxyl group in one molecule, and a compound having one reactive group other than an alcoholic hydroxyl group that reacts with an epoxy group A carboxyl group-containing photosensitive resin obtained by reacting the reaction product with a saturated or unsaturated polybasic acid anhydride,
(8) Saturated or unsaturated polybasic with respect to the primary hydroxyl group in the modified oxetane resin obtained by reacting an unsaturated monocarboxylic acid with a polyfunctional oxetane compound having at least two oxetane rings in one molecule. A carboxyl group-containing photosensitive resin obtained by reacting an acid anhydride, and
(9) 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, and further, one oxirane ring and one or more in the molecule Examples thereof include, but are not limited to, a carboxyl group-containing photosensitive resin obtained by reacting a compound having an ethylenically unsaturated group.
これらの例示の中で好ましいものとしては、上記（２）及び（３）の分子中にエチレン性不飽和二重結合を有するカルボキシル基含有感光性樹脂が、光硬化性、焼成性の面から好ましい。 Among these examples, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecules (2) and (3) is preferable from the viewpoint of photocurability and baking properties. .
なお、本明細書において、（メタ）アクリレートとは、アクリレート、メタクリレート及びそれらの混合物を総称する用語で、他の類似の表現についても同様である。 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.
上記のようなカルボキシル基含有樹脂（Ａ）は、バックボーン・ポリマーの側鎖に多数の遊離のカルボキシル基を有するため、希アルカリ水溶液による現像が可能になる。 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.
また、上記カルボキシル基含有樹脂（Ａ）の酸価は、４０〜２００ｍｇＫＯＨ／ｇの範囲であり、より好ましくは４５〜１２０ｍｇＫＯＨ／ｇの範囲である。カルボキシル基含有樹脂の酸価が４０ｍｇＫＯＨ／ｇ未満であるとアルカリ現像が困難となり、一方、２００ｍｇＫＯＨ／ｇを超えると現像液による露光部の溶解が進むために、必要以上にラインが痩せ、場合によっては、露光部と未露光部の区別なく現像液で溶解剥離してしまい、正常なレジストパターンの描画が困難となるので好ましくない。 Moreover, the acid value of the said carboxyl group-containing resin (A) is the range of 40-200 mgKOH / g, More preferably, it is the range of 45-120 mgKOH / g. If the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, if it exceeds 200 mgKOH / g, dissolution of the exposed portion by the developer proceeds, and the line becomes thinner than necessary. Is unfavorable because it will be dissolved and peeled off with a developer without distinction between exposed and unexposed areas, making it difficult to draw a normal resist pattern.
また、上記カルボキシル基含有樹脂（Ａ）の重量平均分子量は、樹脂骨格により異なるが、一般的に２，０００〜１５０，０００、さらには５，０００〜１００，０００の範囲にあるものが好ましい。重量平均分子量が２，０００未満であると、タックフリー性能が劣ることがあり、露光後の塗膜の耐湿性が悪く現像時に膜減りが生じ、解像度が大きく劣ることがある。一方、重量平均分子量が１５０，０００を超えると、現像性が著しく悪くなることがあり、貯蔵安定性が劣ることがある。 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.
このようなカルボキシル基含有樹脂（Ａ）の配合量は、全組成物中に、好ましくは５〜５０質量％、より好ましくは１０〜３０質量％である。配合量が少なすぎると、塗膜強度が低下したりするので好ましくない。一方、多すぎると、粘性が高くなり、塗布性等が低下するので好ましくない。 The blending amount of such a carboxyl group-containing resin (A) is preferably 5 to 50% by mass and more preferably 10 to 30% by mass in the entire composition. If the blending amount is too small, the coating film strength decreases, which is not preferable. On the other hand, when the amount is too large, the viscosity becomes high, and the coating property and the like are lowered, which is not preferable.
（Ｂ）ガラスフリット
本発明の黒色ペースト組成物に用いられるガラスフリット（Ｂ）としては、軟化点が３００〜６００℃の低融点ガラスフリットが用いられ、酸化鉛、酸化ビスマス、又は酸化亜鉛を主成分とするものが好適に使用できる。また、解像度の点から平均粒径２０μｍ以下のもの、好ましくは５μｍ以下のものを用いることが好ましい。酸化鉛を主成分とするガラス粉末の好ましい例としては、酸化物基準の質量％で、ＰｂＯが４８〜８２％、Ｂ２０３が０．５〜２２％、ＳｉＯ２が３〜３２％、Ａｌ２Ｏ３が０〜１２％、ＢａＯが０〜１０％、ＺｎＯが０〜１５％、ＴｉＯ２が０〜２．５％、Ｂｉ２Ｏ３が０〜２５％の組成を有し、軟化点が４２０〜５９０℃である非結晶性フリットが挙げられる。
(B) Glass frit As the glass frit (B) used in the black paste composition of the present invention, a low-melting glass frit having a softening point of 300 to 600 ° C. is used, mainly lead oxide, bismuth oxide, or zinc oxide. What is used as a component can be preferably used. From the viewpoint of resolution, it is preferable to use those having an average particle size of 20 μm or less, preferably 5 μm or less. Preferred examples of the glass powder based on lead oxide, in mass percent on the oxide basis, PbO is 48 to 82%, B 2 0 3 is 0.5 to 22%, SiO 2 is from 3 to 32%, Al 2 O 3 has a composition of 0-12%, BaO 0-10%, ZnO 0-15%, TiO 2 0-2.5%, Bi 2 O 3 0-25%, softening Non-crystalline frit having a point of 420 to 590 ° C can be mentioned.
また、酸化ビスマスを主成分とするガラス粉末の好ましい例としては、酸化物基準の質量％で、Ｂｉ２Ｏ３が３５〜８８％、Ｂ２Ｏ３が５〜３０％、ＳｉＯ２が０〜２０％、Ａｌ２Ｏ３が０〜５％、ＢａＯが１〜２５％、ＺｎＯが１〜２０％の組成を有し、軟化点が４２０〜５９０℃である非結晶性フリットが挙げられる。 Preferred examples of the glass powder based on bismuth oxide, in mass percent on the oxide basis, Bi 2 O 3 is 35 to 88%, B 2 O 3 is 5 to 30%, SiO 2 is 0 Examples thereof include an amorphous frit having a composition of 20%, Al 2 O 3 of 0 to 5%, BaO of 1 to 25%, ZnO of 1 to 20%, and a softening point of 420 to 590 ° C.
さらに、酸化亜鉛を主成分とするガラス粉末の好ましい例としては、酸化物基準の質量％で、ＺｎＯが２５〜６０％、Ｋ２Ｏが２〜１５％、Ｂ２Ｏ３が２５〜４５％、ＳｉＯ２が１〜７％、Ａｌ２Ｏ３ が０〜１０％、ＢａＯが０〜２０％、ＭｇＯが０〜１０％の組成を有し、軟化点が４２０〜５９０℃である非結晶性フリットが挙げられる。 Further, preferred examples of the glass powder based on zinc oxide, at a weight percent on the oxide basis, ZnO is 25 to 60%, K 2 O is 2 to 15%, B 2 O 3 is 25% to 45% SiO 2 is 1 to 7%, Al 2 O 3 is 0 to 10%, BaO is 0 to 20%, MgO is 0 to 10%, and the softening point is 420 to 590 ° C. Frit.
このようなガラスフリットの配合量は、好ましくは、全組成物中に１〜２０質量％、より好ましくは２〜１０質量％である。配合量が少なすぎると基材との密着性が劣り、配合量が多すぎると組成物の増粘やゲル化が生じるおそれがあり、何れも好ましくない。 The blending amount of such glass frit is preferably 1 to 20% by mass, more preferably 2 to 10% by mass in the total composition. If the blending amount is too small, the adhesion to the substrate is poor, and if the blending amount is too large, the composition may be thickened or gelled.
（Ｃ）黒色顔料
本発明の黒色ペースト組成物に用いられる黒色顔料（Ｃ）としては、Ｃｕ、Ｆｅ、Ｃｒ、Ｍｎ、Ｃｏ、Ｒｕ、Ｌａ等の単独の金属酸化物及び／又は金属元素２種以上からなる複合酸化物が好適に用いることができ、その平均粒径としては、解像度の点より１０μｍ以下、好ましくは２．５μｍ以下のものを用いる。一方、黒色度の点からは、平均粒径１．０μｍ以下、好ましくは０．０２５μｍ以上、０．６μｍ以下のものが好適である。このような黒色顔料の中で、特に比表面積が１．０〜２０ｍ２／ｇの範囲にある四三酸化コバルト（Ｃｏ３Ｏ４）微粒子を用いることが好ましい。四三酸化コバルト（Ｃｏ３Ｏ４）微粒子は黒色度の点で好適であり、また表面積に関しては、その比表面積が１．０ｍ２／ｇ未満では、露光によるパターン形成の精度が低下し、ラインエッジの直線性、あるいは充分な黒さの焼成皮膜が得られ難くなるためである。一方、２０ｍ２／ｇを超えると、粒子の表面積が大きくなり過ぎて現像の際にアンダーカットを生じやすくなる。
(C) Black pigment As the black pigment (C) used in the black paste composition of the present invention, a single metal oxide such as Cu, Fe, Cr, Mn, Co, Ru, La, and / or two metal elements The composite oxide composed of the above can be suitably used, and the average particle size thereof is 10 μm or less, preferably 2.5 μm or less from the viewpoint of resolution. On the other hand, from the point of blackness, an average particle size of 1.0 μm or less, preferably 0.025 μm or more and 0.6 μm or less is suitable. Among such black pigments, it is particularly preferable to use cobalt trioxide (Co 3 O 4 ) fine particles having a specific surface area of 1.0 to 20 m 2 / g. Cobalt tetroxide (Co 3 O 4 ) fine particles are suitable in terms of blackness. Regarding the surface area, if the specific surface area is less than 1.0 m 2 / g, the accuracy of pattern formation by exposure decreases, and the line This is because it becomes difficult to obtain a fired film having edge linearity 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.
また、黒色顔料（Ｃ）の配合量としては、前記カルボン酸含有樹脂（Ａ）１００質量部当り
１０〜１００質量部の範囲が適当である。上記範囲より少ない場合、焼成後に充分な黒さ
が得られず、好ましくない。一方、上記範囲より多い場合、光透過性が低下し、アンダー
カットを生じ易くなるので、好ましくない。
Moreover, as a compounding quantity of a black pigment (C), the range of 10-100 mass parts per 100 mass parts of said carboxylic acid 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.
（Ｄ）一分子内に少なくとも一つ以上のラジカル重合性不飽和基を有する化合物
本発明に用いられる前記一分子内に少なくとも一つ以上のラジカル重合性不飽和基を有する化合物（Ｄ）としては、２−ヒドロキシエチルアクリレート、２−ヒドロキシプロピルアクリレート、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールペンタアクリレートなどのヒドロキシアルキルアクリレート類；エチレングリコール、メトキシテトラエチレングリコール、ポリエチレングリコール、プロピレングリコールなどのグリコールのモノ又はジアクリレート類；Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ−メチロールアクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピルアクリルアミドなどのアクリルアミド類；Ｎ，Ｎ−ジメチルアミノエチルアクリレート、Ｎ，Ｎ−ジメチルアミノプロピルアクリレートなどのアミノアルキルアクリレート類；ヘキサンジオール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリス−ヒドロキシエチルイソシアヌレートなどの多価アルコール又はこれらのエチレオキサイド付加物もしくはプロピレンオキサイド付加物などの多価アクリレート類；フェノキシアクリレート、ビスフェノールＡジアクリレート、及びこれらのフェノール類のエチレンオキサイド付加物もしくはプロピレンオキサイド付加物などのアクリレート類；グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、トリグリシジルイソシアヌレートなどのグリシジルエーテルのアクリレート類；上記ヒドロキシアルキルアクリレートのイソシアネート変成物である多官能もしくは単官能ポリウレタンアクリレート；及びメラミンアクリレート、及び／又は上記アクリレートに対応する各メタクリレートなどが挙げられ、これらは単独又は２種類以上を組み合わせて用いることができる。これらの中で、特に一分子内に少なくとも二つ以上のラジカル重合性不飽和基を有する化合物、例えば、ペンタエリストールトリアクリレート、ジペンタエリスリトールヘキサアクリレートなどが、光硬化性に優れ、好ましい。
(D) Compound having at least one radically polymerizable unsaturated group in one molecule As compound (D) having at least one radically polymerizable unsaturated group in one molecule used in the present invention, Hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate; mono- or di-glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol Acrylates; acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide, and N, N-dimethylaminopropylacrylamide; N, N-dimethylaminoethylamine Aminoalkyl acrylates such as acrylate, N, N-dimethylaminopropyl acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or their ethylene oxide adducts or Polyvalent acrylates such as propylene oxide adducts; Phenoxy acrylate, bisphenol A diacrylate, and acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; glycerin diglycidyl ether, glycerin triglycidyl ether, tri Aglycol ethers such as methylolpropane triglycidyl ether and triglycidyl isocyanurate Polyfunctional or monofunctional polyurethane acrylate which is an isocyanate modification of the above hydroxyalkyl acrylate; and melamine acrylate, and / or each methacrylate corresponding to the above acrylate, and the like. These may be used alone or in combination of two or more. Can be used. Among these, compounds having at least two radically polymerizable unsaturated groups in one molecule, such as pentaerythritol triacrylate and dipentaerythritol hexaacrylate, are particularly preferable because of excellent photocurability.
尚、以下、この化合物を、重合性モノマーと略す場合がある。 Hereinafter, this compound may be abbreviated as a polymerizable monomer.
このような一分子内に少なくとも一つ以上のラジカル重合性不飽和基を有する（Ｄ）の配合量は、前記カルボキシル基含有樹脂（Ａ）１００質量部に対して、好ましくは１０〜１２０質量部、より好ましくは、２０〜１００質量部の割合である。前記配合量が、少なすぎると、光硬化性が低下し、活性エネルギー線照射後のアルカリ現像により、パターン形成が困難となるので、好ましくない。一方、多すぎると、アルカリ水溶液に対する溶解性が低下して、塗膜が脆くなるので、好ましくない。 The blending amount of (D) having at least one radical polymerizable unsaturated group in one molecule is preferably 10 to 120 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). The ratio is more preferably 20 to 100 parts by mass. If the blending amount is too small, the photocurability decreases, and pattern formation becomes difficult by alkali development after irradiation with active energy rays, which is not preferable. On the other hand, when the amount is too large, the solubility in an aqueous alkali solution is lowered, and the coating film becomes brittle.
（Ｅ）光重合開始剤
（Ｅ−１）オキシムエステル系光重合開始剤
本発明の黒色ペースト組成物に用いられる光重合開始剤（Ｅ）としては、前記一般式（ＩＩ）で表わされる官能基を有するオキシムエステル系光重合開始剤（Ｅ−１）を用いることが、ＬＤＩ用黒色ペースト組成物として必須である。オキシムエステル系光重合開始剤の具体例としては、１，２−オクタンジオン−１−［４−（フェニルチオ）−２−（Ｏ−ベンゾイルオキシム）］、エタノン−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−１−（Ｏ−アセチルオキシム）、及び下記式（Ｖ）で表わされる２−（アセチルオキシイミノメチル）チオキサンテン−９−オンが挙げられる。これらの中で、下記式（Ｖ）で表される化合物、２−（アセチルオキシイミノメチル）チオキサンテン−９−オンが、特に好ましい。市販品としては、チバ・スペシャルティ・ケミカルズ社製のＣＧＩ−３２５がある。
(E) Photopolymerization initiator (E-1) Oxime ester photopolymerization initiator As the photopolymerization initiator (E) used in the black paste composition of the present invention, a functional group represented by the general formula (II) is used. It is essential as a black paste composition for LDI to use an oxime ester photopolymerization initiator (E-1) having Specific examples of the oxime ester photopolymerization initiator include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) and 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the following formula (V) are mentioned. It is done. Among these, a compound represented by the following formula (V), 2- (acetyloxyiminomethyl) thioxanthen-9-one, is particularly preferable. A commercially available product is CGI-325 manufactured by Ciba Specialty Chemicals.
このようなオキシムエステル系光重合開始剤（Ｅ−１）の配合量としては、前記カルボキシル基含有樹脂（Ａ）１００質量部に対して、好ましくは０．０１〜２０質量部、より好ましくは０．０１〜５質量部の割合である。オキシムエステル系光重合開始剤（Ｅ−１）の配合量が、前記カルボキシル基含有樹脂（Ａ）１００質量部に対して、少なすぎると、充分な光硬化性が得られないので、好ましくない。一方、多すぎると、厚膜硬化性が低下し、製品のコストアップにつながるので、好ましくない。 As a compounding quantity of such an oxime ester system photoinitiator (E-1), Preferably it is 0.01-20 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (A), More preferably, it is 0. .01 to 5 parts by mass. If the amount of the oxime ester photopolymerization initiator (E-1) is too small relative to 100 parts by mass of the carboxyl group-containing resin (A), sufficient photocurability cannot be obtained, which is not preferable. On the other hand, if the amount is too large, the thick film curability is lowered and the cost of the product is increased, which is not preferable.
（Ｅ−２）フォスフィンオキサイド系光重合開始剤
本発明の黒色ペースト組成物は、さらに高感度化するために、前記一般式（ＩＶ）で表わされる構造を含むフォスフィンオキサイド系光重合開始剤（Ｅ−２）を配合することが好ましい。
(E-2) Phosphine oxide photopolymerization initiator The black paste composition of the present invention is a phosphine oxide photopolymerization initiator containing the structure represented by the general formula (IV) in order to further increase the sensitivity. It is preferable to blend (E-2).
このようなフォスフィンオキサイド系光重合開始剤（Ｅ−２）としては、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス(２，４，６−トリメチルベンゾイル)−フェニルフォスフィンオキサイド、ビス(２，６−ジメトキシベンゾイル)−２，４，４−トリメチル−ペンチルフォスフィンオキサイド、２，４，６−トリメチルベンゾイルフェニルエチルホスフィネートなどが挙げられる。 Examples of such phosphine oxide photopolymerization initiator (E-2) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis ( 2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoylphenyl ethyl phosphinate and the like.
このようなフォスフィンオキサイド系光重合開始剤（Ｅ−２）の配合量としては、前記カルボキシル基含有樹脂（Ａ）１００質量部に対して、好ましくは６０質量部以下、より好ましくは５０質量部以下の割合である。フォスフィンオキサイド系光重合開始剤（Ｅ−２）の配合量が、多すぎると、厚膜硬化性が低下して、製品のコストアップに繋がるので、好ましくない。 As a compounding quantity of such a phosphine oxide type photoinitiator (E-2), Preferably it is 60 mass parts or less with respect to 100 mass parts of said carboxyl group containing resin (A), More preferably, it is 50 mass parts. The ratio is as follows. If the blending amount of the phosphine oxide photopolymerization initiator (E-2) is too large, the thick film curability is lowered and the cost of the product is increased, which is not preferable.
また、前記一般式（ＩＩ）で表わされる官能基を有するオキシムエステル系光重合開始剤（Ｅ−１）の配合量が、上記一般式（IV）で表わされるフォスフィンオキサイド系光重合開始剤（Ｅ−２）の配合量より少ないことが、高感度で厚膜硬化性を得るために、好ましい。 Moreover, the compounding quantity of the oxime ester system photoinitiator (E-1) which has a functional group represented by the said general formula (II) is a phosphine oxide type photoinitiator represented by the said general formula (IV) ( Less than the blending amount of E-2) is preferable in order to obtain a thick film curability with high sensitivity.
（他の光重合開始剤、光開始助剤、増感剤）
本発明組成物は、さらに必要に応じて、公知慣用の光重合開始剤、光開始助剤、増感剤を併用することができる。具体的には、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル等のベンゾインとベンゾインアルキルエーテル類；アセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、２，２−ジエトキシ−２−フェニルアセトフェノン、２，２−ジエトキシ−２−フェニルアセトフェノン、１，１−ジクロロアセトフェノン等のアセトフェノン類；２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１等のアミノアセトフェノン類；２−メチルアントラキノン、２−エチルアントラキノン、２−ターシャリーブチルアントラキノン、１−クロロアントラキノン等のアントラキノン類；２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、２−クロロチオキサントン、２，４−ジイソプロピルチオキサントン等のチオキサントン類；アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類；ベンゾフェノン等のベンゾフェノン類；又はキサントン類；（２，６−ジメトキシベンゾイル）−２，４，４−ペンチルフォスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド、エチル−２，４，６−トリメチルベンゾイルフェニルフォスフィネイト等のフォスフィンオキサイド類などが挙げられる。
(Other photopolymerization initiators, photoinitiators, sensitizers)
In the composition of the present invention, a known and commonly used photopolymerization initiator, photoinitiator assistant, and sensitizer can be used in combination as required. Specifically, benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone , Acetophenones such as 2,2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- Aminoacetophenones such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 1-chloroanthracone Anthraquinones such as thiophene; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenone Or (2,6-dimethoxybenzoyl) -2,4,4-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6 -Phosphine oxides such as trimethylbenzoyldiphenylphosphine oxide and ethyl-2,4,6-trimethylbenzoylphenyl phosphinate.
（Ｆ）前記一般式（Ｉ）で表わされるアルミニウム化合物
このアルミニウム化合物は、ガラスフリットや黒色顔料等の無機粒子の分散安定性を向上させるために配合する。本発明者はその理由を以下のように推測する。このアルミニウム化合物は、ガラスフリット（Ｂ）および黒色顔料（Ｃ）に対して強力に吸着し、大量の溶剤での希釈の際も離脱しにくいためペースト中の無機粒子の凝集、沈降を抑制していると考えられる。
(F) Aluminum compound represented by general formula (I) This aluminum compound is blended in order to improve the dispersion stability of inorganic particles such as glass frit and black pigment. The inventor presumes the reason as follows. This aluminum compound is strongly adsorbed to the glass frit (B) and the black pigment (C), and is difficult to separate even when diluted with a large amount of solvent, and thus suppresses aggregation and sedimentation of inorganic particles in the paste. It is thought that there is.
この化合物を例示すれば、アルミニウムトリス（アセチルアセトネート）、アルミニウムトリス（エチルアセトアセテート）、アルミニウムモノアセチルアセトネートビス（エチルアセトアセテート）、ラウリルアセトアセテートアルミニウムジイソプロピレートなどが挙げられる。 Examples of this compound include aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), aluminum monoacetylacetonate bis (ethylacetoacetate), lauryl acetoacetate aluminum diisopropylate and the like.
このアルミニウム化合物の配合量は、前記カルボキシル基含有樹脂（Ａ）１００質量部に対して、好ましくは０．０１〜１０質量部、より好ましくは０．１〜５質量部の割合である。アルミニウム化合物の配合量が、前記カルボキシル基含有樹脂（Ａ）１００質量部に対して、少なすぎると、希釈時の黒色顔料の凝集が生じやすくなり、分散安定性が確保できなくなる恐れがあるので、好ましくない。一方、多すぎると粘度上昇やゲル化などを生じやすくなるので、好ましくない。 The amount of the aluminum compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). If the compounding amount of the aluminum compound is too small with respect to 100 parts by mass of the carboxyl group-containing resin (A), the black pigment tends to aggregate when diluted, and dispersion stability may not be secured. It is not preferable. On the other hand, if the amount is too large, viscosity increases or gelation tends to occur.
（Ｇ）ホウ酸
さらに、本発明の黒色ペースト組成物は、保存安定性を上げるために、ホウ酸（Ｇ）を加えることが、好ましい。
(G) Boric acid Further, it is preferable to add boric acid (G) to the black paste composition of the present invention in order to increase the storage stability.
このようなホウ酸（Ｇ）は、ジェットミル、ボールミル、ロールミルなどにより微粉化した平均粒経（Ｄ５０）が、２０μｍ以下、好ましくは０．１μｍ以上、５μｍ以下のものが用いられる。このように微粉化したものは、吸湿・再凝集しやすくなるため、粉砕後は速やかに使用することが好ましい。またペースト中に含まれる樹脂や溶剤などとともに粉砕することも出来る。 As such boric acid (G), an average particle size (D 50 ) pulverized by a jet mill, a ball mill, a roll mill or the like is 20 μm or less, preferably 0.1 μm or more and 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.
このようなホウ酸（Ｇ）の配合割合は、前記ガラスフリット（Ｂ）１００質量部に対して、好ましくは０．０１〜１０質量部が適当であり、より好ましくは、０．１〜２質量部である。ホウ酸の配合割合が、前記ガラスフリット（Ｂ）１００質量部に対して、少なすぎると、保存安定性向上効果が無いので、好ましくない。 The blending ratio of such boric acid (G) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the glass frit (B). Part. If the blending ratio of boric acid is too small with respect to 100 parts by mass of the glass frit (B), there is no effect of improving storage stability, which is not preferable.
なお、このようにホウ酸（Ｇ）を配合する場合、２５℃の水１００ｇに対する溶解度が２０ｇ以下の疎水性溶媒を用いる必要がある。水に対する溶解度の高い有機溶媒を用いた場合、有機溶媒中に溶け込んだ水が、ガラスフリット中に含まれる金属をイオン化させ、ゲル化の原因となるので、好ましくない。 When boric acid (G) is blended in this way, it is necessary to use a hydrophobic solvent having a solubility in 100 g of water at 25 ° C. of 20 g or less. When an organic solvent having high solubility in water is used, water dissolved in the organic solvent ionizes the metal contained in the glass frit and causes gelation, which is not preferable.
（Ｈ）リン化合物
さらに、本発明の黒色ペースト組成物の保存安定性をより向上させるために、下記一般式（ＶＩ）又は下記一般式（ＶＩＩ）で表わされる構造を持つリン化合物（Ｈ）を配合させることが好ましい。
(H) Phosphorus Compound Further, in order to further improve the storage stability of the black paste composition of the present invention, a phosphorus compound (H) having a structure represented by the following general formula (VI) or the following general formula (VII) is added. It is preferable to mix.
このようなリン化合物（Ｈ）としては、リン酸メチル、リン酸エチル、リン酸プロピル、リン酸ブチル、リン酸フェニル、リン酸ジメチル、リン酸ジエチル、リン酸ジブチル、リン酸ジプロピル、リン酸ジフェニル、リン酸イソプロピル、リン酸ジイソプロピル、リン酸−ｎ−ブチル、亜リン酸メチル、亜リン酸エチル、亜リン酸プロピル、亜リン酸ブチル、亜リン酸フェニル、亜リン酸ジメチル、亜リン酸ジエチル、亜リン酸ジブチル、亜リン酸ジプロピル、亜リン酸ジフェニル、亜リン酸イソプロピル、亜リン酸ジイソプロピル、亜リン酸ｎ−ブチル−２−エチルヘキシルヒドロキシエチリレンジホスホン酸、アデノシン三リン酸、アデノシンリン酸、モノ（２−メタクリロイルオキシエチル）アシッドホスフェート、モノ（２−アクリロイルオキシエチル）アシッドホスフェート、ジ（２−メタクリロイルオキシエチル）アシッドホスフェート、ジ（２−アクリロイルオキシエチル）アシッドホスフェート、エチルジエチルホスホノアセテート、エチルアシッドホスフェート、ブチルアシッドホスフェート、ブチルピロホスフェート、ブトキシエチルアシッドホスフェート、２−エチルヘキシルアシッドホスフェート、オレイルアシッドホスフェート、テトラコシルアシッドホスフェート、ジエチレングリコールアシッドホスフェート、（２−ヒドロキシエチル）メタクリレートアシッドホスフェート等が挙げられる。これらのリン化合物は、単独又は２種類以上を組み合わせて用いることができる。 Examples of such phosphorus compounds (H) include methyl phosphate, ethyl phosphate, propyl phosphate, butyl phosphate, phenyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dipropyl phosphate, diphenyl phosphate. , Isopropyl phosphate, diisopropyl phosphate, -n-butyl phosphate, methyl phosphite, ethyl phosphite, propyl phosphite, butyl phosphite, phenyl phosphite, dimethyl phosphite, diethyl phosphite , Dibutyl phosphite, dipropyl phosphite, diphenyl phosphite, isopropyl phosphite, diisopropyl phosphite, n-butyl-2-ethylhexyl hydroxyethylenediphosphophosphonic acid, adenosine triphosphate, adenosine phosphorus Acid, mono (2-methacryloyloxyethyl) acid phosphate, mono (2-acrylic acid) Yloxyethyl) acid phosphate, di (2-methacryloyloxyethyl) acid phosphate, di (2-acryloyloxyethyl) acid phosphate, ethyl diethyl phosphonoacetate, ethyl acid phosphate, butyl acid phosphate, butyl pyrophosphate, butoxyethyl acid Examples include phosphate, 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.
これらリン化合物（Ｈ）の配合量としては、前記ガラスフリット（Ｂ）１００質量部に対して、好ましくは１０質量部以下、より好ましくは、０．１〜５質量部である。リン化合物（Ｈ）の配合量が、前記ガラスフリット（Ｂ）１００質量部に対して、多すぎると、焼成性が低下するので、好ましくない。 As a compounding quantity of these phosphorus compounds (H), Preferably it is 10 mass parts or less with respect to 100 mass parts of said glass frit (B), More preferably, it is 0.1-5 mass parts. If the amount of the phosphorus compound (H) is too large with respect to 100 parts by mass of the glass frit (B), the calcination property is lowered, which is not preferable.
（その他添加物）
本発明の黒色ペースト組成物は、前記カルボキシル基含有樹脂（Ａ）の合成や組成物の調整のため、又は基板やキャリアフィルムに塗布するための粘度調整のため、有機溶剤を使用することができる。具体的には、メチルエチルケトン、シクロヘキサノンなどのケトン類；トルエン、キシレン、テトラメチルベンゼンなどの芳香族炭化水素類；セロソルブ、メチルセロソルブ、カルビトール、メチルカルビトール、ブチルカルビトール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、トリエチレングリコールモノエチルエーテルなどのグリコールエーテル類；酢酸エチル、酢酸ブチル、セロソルブアセテート、ブチルセロソルブアセテート、カルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテルアセテートなどの酢酸エステル類；エタノール、プロパノール、エチレングリコール、プロピレングリコール、テルピネオールなどのアルコール類；オクタン、デカンなどの脂肪族炭化水素；石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサなどの石油系溶剤が挙げられ、これらは単独又は２種類以上を組み合わせて用いることができる。
(Other additives)
The black paste composition of the present invention can use an organic solvent for the synthesis of the carboxyl group-containing resin (A), the adjustment of the composition, or the viscosity adjustment for application to a substrate or a carrier film. . Specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, di Glycol ethers such as propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol Acetates, acetates such as propylene glycol monomethyl ether acetate; ethanol, Examples include alcohols such as lopanol, ethylene glycol, propylene glycol, and terpineol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. Two or more types can be used in combination.
本発明の黒色ペースト組成物は、さらに必要に応じて、ハイドロキノン、ハイドロキノンモノメチルエーテル、ｔ−ブチルカテコール、ピロガロール、フェノチアジンなどの公知慣用の熱重合禁止剤、微粉シリカ、有機ベントナイト、モンモリロナイトなどの公知慣用の増粘剤、シリコーン系、フッ素系、高分子系などの消泡剤及び／又はレベリング剤、イミダゾール系、チアゾール系、トリアゾール系等のシランカップリング剤などのような公知慣用の添加剤類を配合することができる。 If necessary, the black paste composition of the present invention may be a known conventional thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, etc. Conventional additives such as thickeners, silicone-based, fluorine-based, polymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, etc. Can be blended.
（組成物の使用）
以上説明したような本発明の黒色ペースト組成物は、例えば前記有機溶剤で塗布方法に適した粘度に調整し、基板上に、ディップコート法、フローコート法、ロールコート法、バーコーター法、スクリーン印刷法、カーテンコート法、スピンコート法、ダイコート法等の方法により塗布し、例えば約６０〜１２０℃で５〜４０分程度乾燥させることにより、タックフリーの塗膜を形成できる。本発明の黒色ペースト組成物の粘度は塗布方法に応じて任意に調整可能であるが、ダイコート法、スピンコート法などの低粘度液体を用いる塗布方法の場合、組成物の粘度は１０〜２００ｍＰａ・ｓ、好ましくは、１５〜１００ｍＰａ・ｓの範囲が好適である。粘度が１０ｍＰａ・ｓより低いと多量の希釈溶剤の影響により分散安定性の確保が困難となるので好ましくない。一方、２００ｍＰａ・ｓより高いとダイコート法、スピンコート法での塗布が困難となり塗布性が低下するため好ましくない。なお、本発明における粘度とは、コーンプレート粘度計を用い２５℃にて測定した値である。又は、上記組成物をキャリアフィルム上に塗布し、乾燥させてフィルムとして巻き取ったものを基板上にラミネートすることにより、タックフリーの塗膜を形成できる。
(Use of composition)
The black paste composition of the present invention as described above is adjusted to a viscosity suitable for the coating method using, for example, the organic solvent, and the dip coating method, flow coating method, roll coating method, bar coater method, screen on the substrate. A tack-free coating film can be formed by coating by a method such as a printing method, a curtain coating method, a spin coating method, a die coating method, and the like, and drying at about 60 to 120 ° C. for about 5 to 40 minutes. The viscosity of the black paste composition of the present invention can be arbitrarily adjusted according to the coating method, but in the case of a coating method using a low-viscosity liquid such as a die coating method or a spin coating method, the viscosity of the composition is 10 to 200 mPa · s, preferably in the range of 15 to 100 mPa · s. If the viscosity is lower than 10 mPa · s, it is difficult to ensure dispersion stability due to the influence of a large amount of diluent solvent, which is not preferable. On the other hand, if it is higher than 200 mPa · s, coating by the die coating method or spin coating method becomes difficult and coating properties are lowered, which is not preferable. The viscosity in the present invention is a value measured at 25 ° C. using a cone plate viscometer. 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.
なお、このようにして乾燥した塗膜の膜厚１μｍ当りの吸光度は、０．１〜０．８であることが、パターン形成性の面から好ましい。 In addition, it is preferable from the surface of pattern formation property that the light absorbency per 1 micrometer of film thickness of the coating film dried in this way is 0.1-0.8.
その後、接触式（又は非接触方式）により、パターンを形成したフォトマスクを通して選択的に活性エネルギー線により露光し、未露光部を希アルカリ水溶液（例えば０．３〜３％炭酸ソーダ水溶液）により現像してブラックマトリックスパターンが形成される。 Then, the contact type (or non-contact type) is selectively exposed with active energy rays through a photomask having a pattern formed, and the unexposed portion is developed with a dilute alkaline aqueous solution (for example, 0.3 to 3% sodium carbonate aqueous solution). Thus, a black matrix pattern is formed.
上記活性エネルギー線照射に用いられる露光機としては、直接描画装置（例えばコンピューターからのＣＡＤデータにより直接レーザーで画像を描くレーザー・ダイレクト・イメージング装置）を用いることができる。活性エネルギー線源としては、最大波長が３５０ｎｍ〜４２０ｎｍの範囲にあるレーザー光を出すレーザーダイオード、ガスレーザー、固体レーザーなどが挙げられ、特にレーザーダイオードが好ましい。上記直接描画装置としては、例えば日本オルボテック社製、ペンタックス社製、日立ビアメカニクス社製、ボール・セミコンダクター社製等のものを使用することができ、いずれの装置を用いてもよい。 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.
また、上記直接描画装置以外にも、従来の露光機を用いることもできる。その光源としては、ハロゲンランプ、高圧水銀灯、レーザー光、メタルハライドランプ、ブラックランプ、無電極ランプなどが使用される。 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.
また、前記現像には、スプレー法、浸漬法等が用いられる。現像液としては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、珪酸ナトリウムなどの金属アルカリ水溶液や、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、テトラメチルアンモニウムハイドロオキシドなどのアミン水溶液、特に約１．５質量％以下の濃度の希アルカリ水溶液が好適に用いられるが、組成物中のカルボキシル基含有樹脂（Ａ）のカルボキシル基がケン化され、未硬化部（未露光部）が除去されればよく、上記のような現像液に限定されるものではない。また、現像後に不要な現像液の除去のため、水洗や酸中和を行なうことが好ましい。 For the development, a spray method, a dipping method or the like is used. Developers include aqueous metal alkali solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium silicate, and aqueous amine solutions such as monoethanolamine, diethanolamine, triethanolamine, and tetramethylammonium hydroxide. A dilute alkaline aqueous solution having a concentration of 1.5% by mass or less is preferably used, but the carboxyl group of the carboxyl group-containing resin (A) in the composition is saponified and the uncured part (unexposed part) is removed. The developer is not limited to the developer as described above. Further, it is preferable to perform washing with water and acid neutralization in order to remove unnecessary developer after development.
上記現像によりブラックマトリックスパターン形成された基板は、空気中又は窒素雰囲気下、約４００〜６００℃で焼成することにより、所望のブラックマトリックスパターンを形成することができる。 The substrate on which the black matrix pattern is formed by the above development can be baked at about 400 to 600 ° C. in air or in a nitrogen atmosphere to form a desired black matrix pattern.
以下に実施例および比較例を示して本発明について具体的に説明するが、本発明が下記実施例に限定されるものではないことはもとよりである。 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.
（レーザー露光）
合成例１：カルボキシル基含有樹脂の合成
温度計、攪拌機、滴下ロート、及び還流冷却器を備えたフラスコに、メチルメタクリレートとメタクリル酸を０．８７：０．１３ のモル比で仕込み、溶媒としてジプロピレングリコールモノメチルエーテル、触媒としてアゾビスイソブチロニトリルを入れ、窒素雰囲気下、８０℃で６時間攪拌し、カルボキシル基含有樹脂溶液を得た。この樹脂は、重量平均分子量が約１０，０００、酸価が７４ｍｇＫＯＨ／ｇであった。なお、得られた共重合樹脂の重量平均分子量の測定は、（株）島津製作所製ポンプＬＣ−６ＡＤと昭和電工（株）製カラムＳｈｏｄｅｘ（登録商標）ＫＦ−８０４，ＫＦ−８０３，ＫＦ−８０２を三本つないだ高速液体クロマトグラフィーにより測定した。以下、このカルボキシル基含有樹脂溶液を、Ａ−１ワニスと称す。
(Laser exposure)
Synthesis Example 1: Synthesis of carboxyl group-containing resin Methyl methacrylate and methacrylic acid were charged 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 disolvent was used as a solvent. Propylene glycol monomethyl ether and azobisisobutyronitrile as a catalyst were added and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere to obtain a carboxyl group-containing resin solution. This resin had a weight average molecular weight of about 10,000 and an acid value of 74 mgKOH / g. In addition, the measurement of the weight average molecular weight of the obtained copolymer resin is Shimadzu Corporation pump LC-6AD, Showa Denko Co., Ltd. column Shodex (trademark) KF-804, KF-803, KF-802. Was measured by high performance liquid chromatography. Hereinafter, this carboxyl group-containing resin solution is referred to as A-1 varnish.
合成例２：カルボキシル基含有感光性樹脂の合成
温度計、攪拌機、滴下ロート、及び還流冷却器を備えたフラスコに、メチルメタクリレートとメタクリル酸の仕込み比をモル比で０．７６：０．２４とし、溶媒としてジプロピレングリコールモノメチルエーテル、触媒としてアゾビスイソブチロニトリルを入れ、窒素雰囲気下、８０℃で６時間攪拌し、カルボキシル基含有樹脂溶液を得た。このカルボキシル基含有樹脂溶液を冷却し、重合禁止剤としてメチルハイドロキノン、触媒としてテトラブチルホスホニウムブロミドを用い、グリシジルメタクリレートを、９５〜１０５℃で１６時間の条件で、上記樹脂のカルボキシル基１モルに対し０．１２モルの割合の付加モル比で付加反応させ、冷却後取り出した。上記反応により生成したカルボキシル基含有感光性樹脂の重量平均分子量は約１０，０００、酸価は５９ｍｇＫＯＨ／ｇ、二重結合当量は９５０であった。以下、このカルボキシル基含有感光性樹脂溶液を、Ａ−２ワニスと称す。
Synthesis Example 2: Synthesis of carboxyl group-containing photosensitive resin In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, the charge ratio of methyl methacrylate and methacrylic acid was adjusted to 0.76: 0.24 in molar ratio. Dipropylene glycol monomethyl ether as a solvent and azobisisobutyronitrile as a catalyst were added and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere to obtain a carboxyl group-containing resin solution. This carboxyl group-containing resin solution is cooled, methylhydroquinone is used as a polymerization inhibitor, tetrabutylphosphonium bromide is used as a catalyst, and glycidyl methacrylate is added at 95 to 105 ° C. for 16 hours with respect to 1 mol of carboxyl groups of the resin. The addition reaction was carried out at an addition molar ratio of 0.12 mol, and the mixture was taken out after cooling. The weight average molecular weight of the carboxyl group-containing photosensitive resin produced by the above reaction was about 10,000, the acid value was 59 mgKOH / g, and the double bond equivalent was 950. Hereinafter, this carboxyl group-containing photosensitive resin solution is referred to as A-2 varnish.
実施例１〜１０及び比較例１
前記合成例１、２で得られたＡ−１ワニス及びＡ−２ワニスを用いた表１に示す配合成分を、３本ロールミルで混練し、黒色ペースト組成物を得た。なお、実施例および比較例の黒色ペーストの粘度は２０〜６０ｃｐｓ（ｍＰａ・ｓ）の範囲であった。
Examples 1 to 10 and Comparative Example 1
The compounding components shown in Table 1 using the A-1 varnish and A-2 varnish obtained in Synthesis Examples 1 and 2 were kneaded with a three-roll mill to obtain a black paste composition. In addition, the viscosity of the black paste of an Example and a comparative example was the range of 20-60 cps (mPa * s).
備考
※1： PbO 60%, B2O3 20%、SiO2 15%、Al2O3 5%の組成を有し、熱膨張係数α300=70x10-7/℃、
ガラス点移転445℃の性質のものを、粉砕して平均粒径1.6μmとしたもの
※2： 最大教径が5μm以下で平均粒径が0.2μmの四三酸化コバルト黒色粒子をトリプロピレングリコールモノメチル
エーテル中、濃度70%で均一に分散したスラリー
※3： ペンタエリスリトールトリアクリレート
※4： 2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノプロパン-1-オン
※5： 2-(アセチルオキシイミノメチル)チオキサンテン-9-オン
※6： エタノン、1-[9−エチル-6-(2−メチルベンゾイル)-9H-カルバゾール-3-イル]-、1-(Ｏ−アセチルオキシム)
※7： 2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイド
※8： ラウリルアセトアセテートアルミニウムジイソプロピレート
※9： ジェットミルで平均粒径5μm以下に粉砕したホウ酸
※10： 2-メタクリロイルオキシエチルアシッドホスフェート
※11： プロピレングリコールモノメチルエーテルアセテート
上記実施例１〜１０及び比較例１の黒色ペースト組成物を用い、ガラス基板上にスピンコーターを用いて全面に塗布した。次に、熱風循環式乾燥炉を用い、９０℃で２０分間乾燥して指触乾燥性の良好な皮膜を形成した。次いで、ライン幅１００μｍ、スペース幅１５０μｍとなるストライプ状のＣＡＤデータを用いて、光源として中心波長が４０５ｎｍの青紫色レーザーを有するレーザー・ダイレクト・イメージング露光装置（ペンタックス社製 ＤＩ−μ１０）にて、組成物上の積算光量が４０ｍＪ／ｃｍ２となるよう露光した。その後、液温３０℃の０．４ｗｔ％Ｎａ２ＣＯ３水溶液を用いて２０秒間現像を行い、水洗した。最後に電気炉を用いて空気中にて焼成した。
Remarks * 1: PbO 60%, B 2 O 3 20%, SiO 2 15%, Al 2 O 3 5% composition, thermal expansion coefficient α300 = 70x10 -7 / ℃,
Particles with a glass point transfer of 445 ° C, pulverized to an average particle size of 1.6μm * 2: Tripropylene glycol monomethyl trioxide cobalt trioxide black particles with a maximum diameter of 5μm or less and an average particle size of 0.2μm Slurry uniformly dispersed at a concentration of 70% in ether * 3: Pentaerythritol triacrylate * 4: 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one * 5: 2 -(Acetyloxyiminomethyl) thioxanthen-9-one * 6: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyl) Oxime)
* 7: 2,4,6-Trimethylbenzoyldiphenylphosphine oxide * 8: Lauryl acetoacetate aluminum diisopropylate * 9: Boric acid pulverized by jet mill to an average particle size of 5 μm or less * 10: 2-Methacryloyloxyethyl acid Phosphate * 11: Propylene glycol monomethyl ether acetate The black paste compositions of Examples 1 to 10 and Comparative Example 1 were used and applied onto the entire surface of the glass substrate using a spin coater. Next, it dried for 20 minutes at 90 degreeC using the hot-air circulation type drying furnace, and formed the film | membrane with favorable touch-drying property. Next, using a striped CAD data having a line width of 100 μm and a space width of 150 μm, a laser direct imaging exposure apparatus (DI-μ10 manufactured by Pentax) having a blue-violet laser having a central wavelength of 405 nm as a light source, It exposed so that the integrated light quantity on a composition might be 40 mJ / cm < 2 >. Thereafter, development was carried out for 20 seconds using a 0.4 wt% Na 2 CO 3 aqueous solution having a liquid temperature of 30 ° C., followed by washing with water. Finally, it was fired in air using an electric furnace.
なお、焼成は室温から５９０℃まで５℃／分の昇温速度で昇温し、５９０℃で１０分間保持し、その後室温まで放冷する工程を行なった。 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.
このようにして得られた各基板の各種特性について評価した結果を、表２に示した。 Table 2 shows the results of the evaluation of various characteristics of the substrates thus obtained.
なお、表２中の評価方法は以下の通りである。 The evaluation methods in Table 2 are as follows.
（１）分散安定性
５０ｍＬのサンプル瓶に前記組成物を入れ、室温で２日間放置し、黒色顔料、ガラスフリットの沈降の有無を目視にて評価した。評価基準は以下の通りである。
(1) Dispersion stability The composition was placed in a 50 mL sample bottle and allowed to stand at room temperature for 2 days, and the presence or absence of sedimentation of the black pigment and glass frit was visually evaluated. The evaluation criteria are as follows.
○：沈降が見られない
△：若干の沈降が見られる
×：黒色顔料及びガラススリットが沈降し、上澄みが透明である
（２）吸光度の測定
ソーダライムガラスに乾燥膜厚５μｍおよび１０μｍの塗膜を形成した評価基板の吸光度を、紫外可視分光光度計を用いて測定した。得られたデータから、４０５ｎｍにおける厚さ１μｍあたりの吸光度を算出した。
○: No sedimentation is observed Δ: Some sedimentation is observed ×: The black pigment and the glass slit are sedimented and the supernatant is transparent (2) Measurement of absorbance Coating films with dry film thickness of 5 μm and 10 μm on soda lime glass The absorbance of the evaluation substrate on which was formed was measured using an ultraviolet-visible spectrophotometer. From the obtained data, the absorbance per 1 μm thickness at 405 nm was calculated.
（３）レーザー感光性の評価
Ｌ／Ｓ＝１００／１５０μｍのラインを積算光量５０ｍＪ／ｃｍ２にて露光し、液温３０℃の０．４ｗｔ％Ｎａ２ＣＯ３水溶液を用いて２０秒間現像を行い、光学顕微鏡にてラインが形成できたかどうかを評価した。評価基準は以下の通りである。
(3) Evaluation of Laser Photosensitivity A line of L / S = 100/150 μm is exposed with an integrated light amount of 50 mJ / cm 2 and developed for 20 seconds using a 0.4 wt% Na 2 CO 3 aqueous solution with a liquid temperature of 30 ° C. And evaluated whether a line could be formed with an optical microscope. The evaluation criteria are as follows.
○：全く欠損が見られない。 ○: No defect is observed at all.
△：若干の欠損が見られる。 Δ: Some defects are observed.
×：ラインが形成できない。 X: A line cannot be formed.
（４）最低露光量の算出
積算光量を変えて露光を行い、Ｌ／Ｓ＝１００／１５０μｍのラインが欠損無く形成できる最小の露光量を測定した。なお、比較例は必要露光量が極めて大きく、実用的ではないので、以後の試験は実施しなかった（なお、表２には「−」で示している）。
(4) Calculation of minimum exposure amount Exposure was performed by changing the integrated light amount, and the minimum exposure amount at which a line of L / S = 100/150 μm could be formed without defects was measured. In addition, since the required exposure amount was very large and was not practical in the comparative example, the subsequent test was not performed (indicated by “-” in Table 2).
（５）パターン形成後のライン形状
前記の最低露光量にて露光した場合の、アルカリ現像型の黒色ペースト組成物における現像後のパターンを顕微鏡で観測し、ラインに不規則なばらつきがなく、よれ等がないかどうかで評価した。評価基準は以下のとおりである。
(5) Line shape after pattern formation The pattern after development in the alkali development type black paste composition when exposed at the above minimum exposure amount is observed with a microscope, and there is no irregular variation in the line. It evaluated by whether there was no etc. The evaluation criteria are as follows.
○：不規則なばらつきがなく、よれ等がない。 ○: There is no irregular variation and there is no twist.
△：若干不規則なばらつき、よれ等がある。 (Triangle | delta): There are some irregular variations, a twist, etc.
×：不規則なばらつき、よれ等がある。 X: Irregular variation, warping, etc.
（６）焼成後のライン形状
焼成後のライン形状は、焼成まで終了したパターンを顕微鏡で観測し、ラインに不規則なばらつきがなく、よれ等がないかどうかで評価した。評価基準は以下のとおりである。
(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.
○：不規則なばらつきがなく、よれ等がない。 ○: There is no irregular variation and there is no twist.
△：若干不規則なばらつき、よれ等がある。 (Triangle | delta): There are some irregular variations, a twist, etc.
×：不規則なばらつき、よれ等がある。 X: Irregular variation, warping, etc.
（７）密着性
密着性は、セロハン粘着テープによるピーリングを行い、パターンの剥離がないかどうかで評価した。評価基準は以下のとおりである。
(7) Adhesiveness Adhesiveness was evaluated by peeling with a cellophane adhesive tape and checking for pattern peeling. The evaluation criteria are as follows.
○：パターンの剥離がない。 ○: No pattern peeling.
△：若干パターンの剥離がある。 Δ: There is a slight pattern peeling.
×：パターンの剥離がよくある。 X: The pattern peels frequently.
表２が示す結果から明らかなように、本発明の黒色ペースト組成物は、レーザー光に対する十分な感度を有し、高精細のパターンを形成できることがわかる。 As is clear from the results shown in Table 2, it can be seen that the black paste composition of the present invention has sufficient sensitivity to laser light and can form a high-definition pattern.
（ランプ式露光）
続いて、ランプ式露光でのパターン形成も実施した。上記実施例１〜１０及び比較例１の黒色ペーストを用い、ガラス基板上にスピンコーターを用いて前面に塗布した。次に、熱風循環式乾燥炉を用い、９０℃で２０分間乾燥して指触乾燥性の良好な皮膜を形成した。次いで、ライン幅１００μｍ、スペース幅１５０μｍとなるストライプ状のネガパターンが形成されたガラス乾板をフォトマスクとして用い、光源として超高圧水銀灯を備えた露光装置（伯東社製 ＭＡＴ−５３０１）にてガラス乾板上の積算光量が５０ｍＪ／ｃｍ２となるよう露光した。その後、液温３０℃の０．４質量％Ｎａ２ＣＯ３水溶液を用いて２０秒間現像を行い、その後水洗した。そして、電気炉を用いて空気中にて焼成した。
(Lamp type exposure)
Subsequently, pattern formation by lamp exposure was also performed. The black pastes of Examples 1 to 10 and Comparative Example 1 were applied to the front surface of the glass substrate using a spin coater. 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 striped negative pattern having a line width of 100 μm and a space width of 150 μm is formed as a photomask, and a glass dry plate using an exposure apparatus (MAT-5301 manufactured by Hakutosha) equipped with an ultrahigh pressure mercury lamp as a light source. It exposed so that the upper integrated light quantity might be 50 mJ / cm < 2 >. Thereafter, development was performed for 20 seconds using a 0.4 mass% Na 2 CO 3 aqueous solution having a liquid temperature of 30 ° C., and then washed with water. And it baked in the air using the electric furnace.
なお、焼成は室温から５９０℃まで５℃／分の昇温速度で昇温し、５９０℃で１０分間焼成し、その後室温まで放冷する工程を行なった。 The firing was performed by raising the temperature from room temperature to 590 ° C. at a rate of 5 ° C./min, firing at 590 ° C. for 10 minutes, and then allowing to cool to room temperature.
このようにして得られた各基板の各種特性について評価した結果を表３に示す。なお、表３中の評価方法は以下の通りである。 Table 3 shows the results of evaluation of various characteristics of the substrates thus obtained. The evaluation methods in Table 3 are as follows.
（８）感光特性（ランプ式露光）の評価
Ｌ／Ｓ＝１００／１５０μｍのラインを積算光量５０ｍＪ／ｃｍ２にて露光し、液温３０℃の０．４ｗｔ％Ｎａ２ＣＯ３水溶液を用いて２０秒間現像を行い、光学顕微鏡にてラインが形成できたかどうかを評価した。評価基準は以下の通りである。
(8) Evaluation of photosensitive characteristics (lamp type exposure) A line of L / S = 100/150 μm is exposed with an integrated light quantity of 50 mJ / cm 2 and a 0.4 wt% Na 2 CO 3 aqueous solution with a liquid temperature of 30 ° C. is used. Development was performed for 20 seconds, and it was evaluated whether or not a line could be formed with an optical microscope. The evaluation criteria are as follows.
○：全く欠損が見られない。 ○: No defect is observed at all.
△：若干の欠損が見られる。 Δ: Some defects are observed.
×：ラインが形成できない。 X: A line cannot be formed.
（９）必要露光量の算出
積算光量を変えて露光を行い、Ｌ／Ｓ＝１００／１５０μｍのラインが欠損なく形成できる最小の露光量を測定した。なお、比較例は必要露光量が極めて大きく、実用的ではないので、以後の試験は実施しなかった（なお、表３には「−」で示している）。
(9) Calculation of required exposure amount Exposure was performed by changing the integrated light amount, and the minimum exposure amount at which a line of L / S = 100/150 μm could be formed without defects was measured. In addition, since the required exposure amount was very large and it was not practical in the comparative example, the subsequent test was not carried out (indicated by “−” in Table 3).
（１０）パターン形成後のライン形状
前記の最小の露光量にて露光した場合の、アルカリ現像型の黒色ペースト組成物における現像後のパターンを顕微鏡で観測し、ラインに不規則なばらつきがなく、よれなどがないかどうかで評価した。評価基準は以下のとおりである。
(10) Line shape after pattern formation When the pattern is exposed at the minimum exposure amount, the pattern after development in the alkali development type black paste composition is observed with a microscope, and there is no irregular variation in the line. Evaluation was made based on whether or not there was any distortion. The evaluation criteria are as follows.
○：不規則なばらつきがなく、よれ等がない。 ○: There is no irregular variation and there is no twist.
△：若干不規則なばらつき、よれ等がある。 (Triangle | delta): There are some irregular variations, a twist, etc.
×：不規則なばらつき、よれ等がある。 X: Irregular variation, warping, etc.
（１１）焼成後のライン形状
焼成後のライン形状は、焼成まで終了したパターンを顕微鏡で観察し、ラインに不規則なばらつきがなく、よれなどがないかどうかで評価した。評価基準は以下の通りである。
(11) 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.
○：不規則なばらつきがなく、よれ等がない。 ○: There is no irregular variation and there is no twist.
△：若干不規則なばらつき、よれ等がある。 (Triangle | delta): There are some irregular variations, a twist, etc.
×：不規則なばらつき、よれ等がある。 X: Irregular variation, warping, etc.
（１２）密着性
密着性は、セロハン粘着テープによるピーリングを行い、パターンの剥離がないかどうかで評価した。評価基準は以下のとおりである。
(12) Adhesiveness Adhesiveness was evaluated by peeling with a cellophane adhesive tape and checking for pattern peeling. The evaluation criteria are as follows.
○：パターンの剥離がない。 ○: No pattern peeling.
△：若干パターンの剥離がある。 Δ: There is a slight pattern peeling.
×：パターンの剥離がよくある。 X: The pattern peels frequently.
表３に示す結果から明らかなように、本発明のアルカリ現像型の黒色ペースト組成物は、光源として超高圧水銀灯を用いた場合でも十分な感度を有し、高精密のパターンを形成できることがわかった。 As is apparent from the results shown in Table 3, the alkali developing type black paste composition of the present invention has sufficient sensitivity even when an ultrahigh pressure mercury lamp is used as the light source, and can form a highly precise pattern. It was.
また、分散安定性に優れた低粘度の黒色ペーストが得られることからダイコートなどの低粘度液体を用いる塗布方法に対応することも可能である。更には、焼成後のライン形状に不規則なバラツキがなく、基材との密着性にも優れるものであった。 In addition, since a low-viscosity black paste having excellent dispersion stability can be obtained, it is possible to cope with a coating method using a low-viscosity liquid such as a die coat. Furthermore, there was no irregular variation in the line shape after firing, and the adhesion to the substrate was excellent.
なお、焼成後の黒さも満足し得るものであり、保存安定性も優れていた。 The blackness after firing was satisfactory, and the storage stability was excellent.
Claims (11)
（式中、Ｒ４は、水素原子、炭素数１〜６のアルキル基、又はフェニル基を表わし、Ｒ５は、水素原子、炭素数１〜６のアルキル基を表す。）
（式中、ｎは、０〜２の整数を表し、ｍは、１〜３の整数を表し、ｎ＋ｍ＝３となる関係にある。また、Ｒ１、Ｒ２は、炭素数１〜２４のアルキル基又はアルコキシ基を表し、
Ｒ３は、炭素数１〜６のアルキル基を表す。） (A) carboxyl group-containing resin, (B) glass frit, (C) black pigment, (D) compound having at least one radical polymerizable unsaturated group in one molecule, (E-1) the following general formula An alkali development type black paste composition for baking comprising an oxime ester photopolymerization initiator having a functional group represented by (II) and an aluminum compound represented by the following general formula (I): object.
(In the formula, R 4 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R 5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
(In the formula, n represents an integer of 0 to 2, m represents an integer of 1 to 3, and n + m = 3, and R 1 and R 2 have 1 to 24 carbon atoms. Represents an alkyl group or an alkoxy group,
R 3 represents an alkyl group having 1 to 6 carbon atoms. )
（式中、１つ又は２つのＲ６は、下記一般式（II）で表わされ（但し、２つのＲ６の場合、Ｒ６が異なる場合を含む）、残りのＲ６は、水素原子、メチル基、フェニル基またはハロゲン原子を表す（但し、Ｒ６がそれぞれ異なる場合を含む）。）
（式中、Ｒ４は、水素原子、炭素数１〜６のアルキル基、又はフェニル基を表わし、Ｒ５は、水素原子、炭素数１〜６のアルキル基を表す。） The oxime ester-based photopolymerization initiator (E-1), for firing of an alkali development type of claim 1, characterized in that an oxime ester-based photopolymerization initiator represented by the following general formula (III) Black paste composition.
(In the formula, one or two R 6 are represented by the following general formula (II) (in the case of two R 6 , including the case where R 6 is different), and the remaining R 6 is a hydrogen atom: , Represents a methyl group, a phenyl group or a halogen atom (provided that R 6 is different from each other).
(In the formula, R 4 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R 5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
（式中、Ｒ７、Ｒ８は、それぞれ独立に、炭素数１〜１０の直鎖状又は分岐状のアルキル基、シクロヘキシル基、シクロペンチル基、アリール基、又はハロゲン原子、アルキル基もしくはアルコキシ基で置換されたアリール基、又はいずれか一方が炭素数１〜２０のカルボニル基を表わす。） The alkali development according to any one of claims 1 to 3 , further comprising (E-2) a phosphine oxide photopolymerization initiator including a structure represented by the following general formula (IV). A black paste composition for firing a mold.
(Wherein R 7 and R 8 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or a halogen atom, an alkyl group or an alkoxy group. A substituted aryl group, or either one represents a carbonyl group having 1 to 20 carbon atoms.)
（１）活性エネルギー線を用い、パターン露光する工程と、
（２）希アルカリ水溶液で現像することにより選択的にパターン形成する工程と、
（３）４００〜６００℃で焼成させる工程と、
を含むことを特徴とするブラックマトリックスパターンの形成方法。 A method for forming a black matrix pattern using the composition according to any one of claims 1 to 6 ,
(1) pattern exposure using active energy rays;
(2) a step of selectively forming a pattern by developing with a dilute alkaline aqueous solution;
(3) a step of firing at 400 to 600 ° C .;
A method for forming a black matrix pattern, comprising:
（１）最大波長が３５０ｎｍ〜４２０ｎｍのレーザー発振光源を用い、パターン描画する工程と、
（２）希アルカリ水溶液で現像することにより選択的にパターン形成する工程と、
（３）４００〜６００℃で焼成させる工程と、
を含むことを特徴とするブラックマトリックスパターンの形成方法。 A method for forming a black matrix pattern using the composition according to any one of claims 1 to 6 ,
(1) a pattern drawing process using a laser oscillation light source having a maximum wavelength of 350 nm to 420 nm;
(2) a step of selectively forming a pattern by developing with a dilute alkaline aqueous solution;
(3) a step of firing at 400 to 600 ° C .;
A method for forming a black matrix pattern, comprising:
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| JP4489566B2 (en) * | 2003-11-27 | 2010-06-23 | 太陽インキ製造株式会社 | Curable resin composition, cured product thereof, and printed wiring board |
| JP2006133338A (en) * | 2004-11-04 | 2006-05-25 | Tokyo Ohka Kogyo Co Ltd | Photosensitive composition for forming light shielding film and black matrix formed of the photosensitive composition for forming light shielding film |
| JP4526964B2 (en) * | 2005-01-27 | 2010-08-18 | 旭化成イーマテリアルズ株式会社 | Photopolymerizable resin laminate, glass substrate with black matrix using the same, and method for producing color filter |
| JP2006268027A (en) * | 2005-02-23 | 2006-10-05 | Jsr Corp | Method for manufacturing plasma display panel and transfer film |
| JP4559892B2 (en) * | 2005-03-28 | 2010-10-13 | 太陽インキ製造株式会社 | Colored photosensitive resin composition and cured product thereof |
| TWI379161B (en) * | 2005-04-01 | 2012-12-11 | Jsr Corp | Radiation sensitive resin composition, method for forming projections and spacers, projections and spacers, and liquid crystal display element with them |
| JP2006309157A (en) * | 2005-04-01 | 2006-11-09 | Jsr Corp | Radiation-sensitive resin composition, protrusion and spacer formed of the same, and liquid crystal display element equipped with them |
-
2007
- 2007-09-27 KR KR1020070097404A patent/KR100895352B1/en not_active IP Right Cessation
- 2007-09-28 CN CN2007101406703A patent/CN101183215B/en not_active Expired - Fee Related
- 2007-10-15 TW TW096138503A patent/TW200834232A/en unknown
- 2007-11-15 JP JP2007297033A patent/JP5183160B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101183215A (en) | 2008-05-21 |
| JP2008146041A (en) | 2008-06-26 |
| CN101183215B (en) | 2011-12-07 |
| TW200834232A (en) | 2008-08-16 |
| KR20080044157A (en) | 2008-05-20 |
| KR100895352B1 (en) | 2009-04-29 |
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