JPS63218957A - Method for forming pattern of dyeable resin film - Google Patents
Method for forming pattern of dyeable resin filmInfo
- Publication number
- JPS63218957A JPS63218957A JP62051882A JP5188287A JPS63218957A JP S63218957 A JPS63218957 A JP S63218957A JP 62051882 A JP62051882 A JP 62051882A JP 5188287 A JP5188287 A JP 5188287A JP S63218957 A JPS63218957 A JP S63218957A
- Authority
- JP
- Japan
- Prior art keywords
- dyeable
- photosensitive resin
- monomer
- film
- nonionic surfactant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011347 resin Substances 0.000 title claims abstract description 23
- 229920005989 resin Polymers 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims description 8
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 16
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 8
- 239000011342 resin composition Substances 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 15
- -1 polyoxyethylene Polymers 0.000 description 14
- 239000000243 solution Substances 0.000 description 8
- 239000000975 dye Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical group 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000000982 direct dye Substances 0.000 description 2
- BONNRKLSQRLNHV-UHFFFAOYSA-N n-methylmethanamine;prop-2-enamide Chemical compound CNC.NC(=O)C=C BONNRKLSQRLNHV-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- FGLRWHNZUBAWJK-MDZDMXLPSA-N (e)-3-(3-hydroxyphenyl)-1-phenylprop-2-en-1-one Chemical compound OC1=CC=CC(\C=C\C(=O)C=2C=CC=CC=2)=C1 FGLRWHNZUBAWJK-MDZDMXLPSA-N 0.000 description 1
- AZXGXVQWEUFULR-UHFFFAOYSA-N 2',4',5',7'-tetrabromofluorescein Chemical compound OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 AZXGXVQWEUFULR-UHFFFAOYSA-N 0.000 description 1
- MLIWQXBKMZNZNF-UHFFFAOYSA-N 2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1C(=CC=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-UHFFFAOYSA-N 0.000 description 1
- UZNOMHUYXSAUPB-UHFFFAOYSA-N 2,6-bis[(4-azidophenyl)methylidene]cyclohexan-1-one Chemical compound C1=CC(N=[N+]=[N-])=CC=C1C=C(CCC1)C(=O)C1=CC1=CC=C(N=[N+]=[N-])C=C1 UZNOMHUYXSAUPB-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- JWCDUUFOAZFFMX-UHFFFAOYSA-N 2-ethenoxy-n,n-dimethylethanamine Chemical compound CN(C)CCOC=C JWCDUUFOAZFFMX-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- WWJCRUKUIQRCGP-UHFFFAOYSA-N 3-(dimethylamino)propyl 2-methylprop-2-enoate Chemical compound CN(C)CCCOC(=O)C(C)=C WWJCRUKUIQRCGP-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 1
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 1
- FLCAEMBIQVZWIF-UHFFFAOYSA-N 6-(dimethylamino)-2-methylhex-2-enamide Chemical compound CN(C)CCCC=C(C)C(N)=O FLCAEMBIQVZWIF-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 235000005513 chalcones Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- VUVZASHBYYMLRC-UHFFFAOYSA-N heptane-2,3-diol Chemical compound CCCCC(O)C(C)O VUVZASHBYYMLRC-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optical Filters (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はガラス等の透明な基材を染料によりストライプ
又はモザイク状又はその他の形状に染色する為の可染性
樹脂膜のパターン形成法に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for forming a pattern of a dyeable resin film for dyeing a transparent substrate such as glass into a stripe, mosaic, or other shape with a dye. It is something.
近年ガラス等の透明基材をストライプ又はモザイク状等
に着色したものが色分解用フィルターとして液晶カラー
ＴＶ又はカラーＴＶ用カメラのカラー化の為に増々需要
が増大しつつある。In recent years, demand for transparent substrates such as glass colored in stripes or mosaic shapes has been increasing as color separation filters for use in colorizing liquid crystal color TVs or cameras for color TVs.
本発明はかかる需要等を満たす為になされたガラス等の
透明基材にストライプ又はモザイク状等に又はその他の
形状に染色する為の可染性樹脂膜のパターン形成法に関
するものである。The present invention relates to a method for forming a pattern of a dyeable resin film for dyeing a transparent substrate such as glass in stripes, mosaics, or other shapes, which has been developed to meet such demands.
（従来の技術）
従来この分野に於いては可染性感光性樹脂組成物が用い
られているが、これら可染性感光性樹脂の用いられ方は
先ず適半な濃度に希釈した溶液をガラス板等に塗布し、
次にマスクを介して露光したのち現像してストライプ又
はモザイク状の可染性樹脂膜を形成させ、これを所定の
分光特性を有する染料により染色する等の操作を繰返す
ことにより色分解用フィルターを作成しているが、この
樹脂膜の現像時に於いては２０〜８０℃の中性〜酸性水
溶液を使用して現像を行っている。(Prior Art) Conventionally, dyeable photosensitive resin compositions have been used in this field, but the method for using these dyeable photosensitive resins is to first dilute a solution to an appropriate concentration and apply it to a glass. Apply it to a board etc.
Next, a color separation filter is created by repeating operations such as exposing to light through a mask, developing it to form a striped or mosaic dyeable resin film, and dyeing this with a dye having predetermined spectral characteristics. When developing this resin film, a neutral to acidic aqueous solution at 20 to 80°C is used.
（発明力ず解決しようとする問題点）
前述のように可染性感光性樹脂組成物をガラス板等に塗
布しマスクを介して露光したのち２０〜８０℃の水を使
用して現像を行うと現像時間が長く、更に解像度が劣る
。又酸性溶液で現像を行うと、現像時間は短縮出来るが
露光部皮膜の膜荒れが生じる等の問題があり、工程の合
理化、収率の点で更に改善が望まれていた。(Problems to be solved without inventiveness) As mentioned above, the dyeable photosensitive resin composition is applied to a glass plate, exposed to light through a mask, and then developed using water at 20 to 80°C. The development time is long and the resolution is inferior. Furthermore, when developing with an acidic solution, the developing time can be shortened, but there are problems such as roughening of the film in the exposed areas, and further improvements have been desired in terms of rationalization of the process and yield.
先に本発明者等はこの目的の為に現像液に非イオン界面
活性剤を添加する方法（特願昭６ｌ−２４５３２０）を
提案したが、技術の進歩は更に高解像度のパターンを有
する可染性樹脂膜の形本発明者等はこれらの問題点を解
決すべく検討を行った結果、
ａ）可染性モノマー囚
ｂ）可染性上ツマー以外の親水性モノマー（ＢＣ）疎水
性モノマー（Ｃ）
より成る共重合体（Ｄ）′
を構成成分とする可染性感光性樹脂組成物を用いて基材
表面に皮膜を設けマスクを用いて露光し、現像液にて現
像する際に、可染性感光性樹脂組成物に予め非イオン界
面活性剤を含有させる事により高解像度の画像を有する
可染性樹脂膜パターンを作成することが可能となり本発
明を完成するに至った。Previously, the present inventors proposed a method of adding a nonionic surfactant to the developer for this purpose (Japanese Patent Application No. 61-245320), but advances in technology have led to the development of dyeable materials with even higher resolution patterns. The present inventors conducted studies to solve these problems, and found that a) dyeable monomers, b) hydrophilic monomers other than dyeable monomers (BC), and hydrophobic monomers (BC). C) When a film is formed on the surface of the substrate using a dyeable photosensitive resin composition containing the copolymer (D)' as a constituent component, exposed using a mask, and developed with a developer, By incorporating a nonionic surfactant into the dyeable photosensitive resin composition in advance, it becomes possible to create a dyeable resin film pattern having a high-resolution image, leading to the completion of the present invention.
即ち本発明の非イオン界面活性剤含有可染性感光性樹脂
組成物を用いると無添加の場合に比して、同一時間で現
像した場合、高解像度のノくターンを有する可染性樹脂
膜が得られる。これは品質の向上及び収率の向上に役立
つ。又この場合非イオン界面活性剤は未露光部への水の
濡れと浸透促進剤として作用し、未露光部樹脂の溶解を
容易にするものと推定される。この為短時間に高解像度
現像を可能にするものと推定される。That is, when the nonionic surfactant-containing dyeable photosensitive resin composition of the present invention is used, a dyeable resin film having a high-resolution pattern can be obtained when developed for the same amount of time, compared to when no additive is used. is obtained. This helps improve quality and yield. Further, in this case, the nonionic surfactant is presumed to act as a wetting and penetration promoter of water into the unexposed areas, thereby facilitating dissolution of the resin in the unexposed areas. Therefore, it is estimated that high-resolution development can be performed in a short time.
又この場合の現像温度は２０〜８０°Ｃが好ましい。Further, the developing temperature in this case is preferably 20 to 80°C.
本発明で用いられる非イオン界面活性剤としてはポリオ
キシエチレンアルキルエーテル及びポリオキシエチレン
アルキルフェノールエーテル系、ンルビタン脂肪酸エス
テル系、ポリオキシエチレンンルビタン脂肪酸エステル
系、ポリオキシエチレンアシルエステル系、オキシエチ
レンオキシプロピレンブロツクボリマー、脂肪酸モノグ
リセライド、等が挙げられる。これらは１種又は２種以
上の混合系でも良い。これら非イオン界面活°性剤の使
用量は共重合体（Ｄ１００部に対して０．０５〜１０部
が好ましく、特に０．１〜５部が好ましい。Nonionic surfactants used in the present invention include polyoxyethylene alkyl ether and polyoxyethylene alkylphenol ether, polyoxyethylene rubitan fatty acid ester, polyoxyethylene rubitan fatty acid ester, polyoxyethylene acyl ester, and oxyethylene oxypropylene. Examples include block polymers, fatty acid monoglycerides, and the like. These may be used alone or in a mixed system of two or more. The amount of these nonionic surfactants to be used is preferably 0.05 to 10 parts, particularly preferably 0.1 to 5 parts, per 100 parts of the copolymer (D).
本発明で用いられる可染性感光性樹脂組成物としては例
えば次のようなものが挙げられる。Examples of the dyeable photosensitive resin composition used in the present invention include the following.
即ち、可染性モノマー囚、親水性モノマー（Ｂ、疎水性
モノマー（Ｃ）より成る共重合体（Ｄ又はこれに感光剤
、例えば４．４′−ジアジドカルコン、２゜６−ビス（
４′−アジドベンザル）シクロヘキサノン、２，６−ビ
ス（４′−アジドベンザル）シクロヘキサノン、２，６
−ビス（４′−アジドベンザル）４−メチルシクロヘキ
サノン、１．３−ビス（４′−アジドベンザル）−２−
プロパノン等を組合せて可染性感光性樹脂組成物とした
もの、又はこの共重合体の）に感光性基例えばシンナモ
イル基、アジド基、アクリル基、スチリルピリジニウム
塩構造又はスチリルキノリウム塩構造等を有する化合物
を反応させて可染性感光性樹脂組成物としたもの等があ
る。可染性モノマー囚、親水性モノマー（Ｄ、疎水性モ
ノマー（ｑよりなる共重合体の）それ自体を可染性感光
性樹脂組成物として用いる場合、モノマーとしてシンナ
モイル基、アジド基、アクリル基、スチリルピリジニウ
ム塩構造又はスチリルキノリウム塩構造等を有するモノ
マーを共重合させて得た可染性感光性樹脂組成物が好ま
しい。That is, a dyeable monomer, a hydrophilic monomer (B), a copolymer (D) consisting of a hydrophobic monomer (C), or a photosensitizer, such as 4,4'-diazide chalcone, 2°6-bis(
4'-azidobenzal)cyclohexanone, 2,6-bis(4'-azidobenzal)cyclohexanone, 2,6
-bis(4'-azidobenzal)4-methylcyclohexanone, 1,3-bis(4'-azidobenzal)-2-
A dyeable photosensitive resin composition prepared by combining propanone, etc., or a copolymer thereof) has a photosensitive group such as a cinnamoyl group, an azide group, an acrylic group, a styrylpyridinium salt structure, or a styrylquinolium salt structure. There are dyeable photosensitive resin compositions made by reacting compounds containing the same. When using the dyeable monomer, a hydrophilic monomer (D, a copolymer consisting of a hydrophobic monomer (Q)) itself as a dyeable photosensitive resin composition, the monomers include a cinnamoyl group, an azide group, an acrylic group, A dyeable photosensitive resin composition obtained by copolymerizing a monomer having a styrylpyridinium salt structure or a styrylquinolium salt structure is preferred.
本発明で用いられる可染性モノマー（Ａｌとしては例え
ば次のものが挙げられる。Examples of the dyeable monomer (Al) used in the present invention include the following.
（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）エチルメタクリレート、（Ｎ、
Ｎ−ジエチルアミノ）エチルアクリレート、（Ｎ、Ｎ−
ジエチルアミノ）エチルメタクリレート、（Ｎ、Ｎ−ジ
メチルアミノ）プロピルアクリルアミド、（Ｎ、Ｎ−ジ
メチルアミノ）プロピルメタクリルアミド、（Ｎ、Ｎ−
ジメチルアミノ）エチルビニルエーテル、（Ｎ、Ｎ−ジ
メチルアミノ）グロビルアクリレート、（Ｎ、Ｎ−ジメ
チルアミノ）プロピルメタクリレート、４−ビニルピリ
ジン、ジアリルアミン、２−ヒドロキシ−３−メタクリ
ロイルオキシグロビル、トリメチルアンモニウムクロラ
イド、メタクリロイルオキシエチルトリメチルアンモニ
ウムクロライド。(N,N-dimethylamino)ethyl acrylate, (N
, N-dimethylamino)ethyl methacrylate, (N,
N-diethylamino)ethyl acrylate, (N,N-
diethylamino)ethyl methacrylate, (N,N-dimethylamino)propylacrylamide, (N,N-dimethylamino)propylmethacrylamide, (N,N-
Dimethylamino)ethyl vinyl ether, (N,N-dimethylamino)globil acrylate, (N,N-dimethylamino)propyl methacrylate, 4-vinylpyridine, diallylamine, 2-hydroxy-3-methacryloyloxyglobil, trimethylammonium chloride , methacryloyloxyethyltrimethylammonium chloride.
又本発明で用いられる親水性モノマー（Ｂ）としては例
えば次のものが挙げられる。Examples of the hydrophilic monomer (B) used in the present invention include the following.
ヒドロキシエチルアクリレート、ヒドロキシエチルメタ
クリレート、アクリルアミド、メタクリルアミド、ビニ
ルピロリドン、Ｎ、Ｎ−ジメチルアクリルアミド。Hydroxyethyl acrylate, hydroxyethyl methacrylate, acrylamide, methacrylamide, vinylpyrrolidone, N,N-dimethylacrylamide.
又本発明で用いられる疎水性モノマー（Ｃ）としてはメ
チルアクリレート、メチルメタクリレート、エチルアク
リレート、スチレン、ｐ−メチルスチレン、ブチルアク
リレート、ブチルメタクリレート等が挙げられる。Examples of the hydrophobic monomer (C) used in the present invention include methyl acrylate, methyl methacrylate, ethyl acrylate, styrene, p-methylstyrene, butyl acrylate, and butyl methacrylate.
これら可染性モノマー囚、親水性モノマーの）、疎水性
モノマー（Ｃ）の配合割合は可染性モノマー（Ａ）１０
〜８０重量％、親水性七ツマ−（Ｂ）２〜６０重量％、
疎水性モノマー（０５〜５０重量％であるものが好まし
い。これらのモノマーは従来技術により重合出来る。The blending ratio of these dyeable monomers, hydrophilic monomers), and hydrophobic monomers (C) is 10% of the dyeable monomer (A).
~80% by weight, 2 to 60% by weight of hydrophilic hexamer (B),
Hydrophobic monomers (05-50% by weight are preferred). These monomers can be polymerized by conventional techniques.
又本発明で用いられる非イオン界面活性剤含有可染性感
光性樹脂組成物はガラス板等に塗布し易くする為に有機
溶剤に希釈されて用いられる。有機溶剤としては例えば
メチルセロソルブ、エチルセロソルフ、エチレングリコ
ールモノエチルエーテルアセテート、ジグライム、メチ
ルイソブチルケトン、トルエン、キシレン、メチルプロ
ピレンジクリコール、プロビルプロピレングリコール、
ブチルプロピレングリコール、等が挙げられる。The nonionic surfactant-containing dyeable photosensitive resin composition used in the present invention is diluted with an organic solvent to make it easier to apply to glass plates and the like. Examples of organic solvents include methyl cellosolve, ethyl cellosolve, ethylene glycol monoethyl ether acetate, diglyme, methyl isobutyl ketone, toluene, xylene, methyl propylene dicricol, probyl propylene glycol,
Butylpropylene glycol, etc. can be mentioned.
この非イオン界面活性剤含有可染性感光性樹脂組成物を
塗布したガラス等の基材はマスクを介して紫外線等によ
り露光される。未露光部は現像液で現像される。現像液
は水でも良いが前記の非イオン界面活性剤を含有する水
溶液を用いる事が好ましい。このようにして現像された
ものは高解像度の可染性樹脂膜パターンを有する基板と
なる。又樹脂の膜厚は例えば０．２〜５０μの任意の厚
さに膜を作成出来る。A base material such as glass coated with this nonionic surfactant-containing dyeable photosensitive resin composition is exposed to ultraviolet light or the like through a mask. The unexposed areas are developed with a developer. The developer may be water, but it is preferable to use an aqueous solution containing the above-mentioned nonionic surfactant. What is developed in this way becomes a substrate having a high-resolution dyeable resin film pattern. Further, the resin film can be formed to have an arbitrary thickness of, for example, 0.2 to 50 μm.
現像された所定のパターンを有するガラス、プラスチッ
ク等の基材はアニオン染料により染色される。A substrate such as glass or plastic having a developed predetermined pattern is dyed with an anionic dye.
アニオン性染料としてはカラーインデックス（５ｏｃｉ
ｅｔｙ ｏｆ Ｄｙｅｒｓ ａｎｄ Ｃｏｌｏｕｒｌｓ
ｔｓ発行）に已Ｉ・Ａｃ１ｄとして記載されている酸性
染料、同じくＣ０１，Ｄｉｒｅｃｔとして記載されてい
る直接染料及び同じ（Ｃ，１，Ｒｅａｃｔｉｖｅとして
記載されている反応性染料等が挙げられるが、特に酸性
染料が好ましい。Color index (5oci) is an anionic dye.
ety of Dyers and Colors
Examples include acid dyes listed as 已I/Ac1d in the same publication), direct dyes also listed as C01, Direct, and reactive dyes listed as C, 1, Reactive, etc. Acidic dyes are preferred.
（実施例）
実施例１゜
ジメチルアミノプロピルアクリルアミド ３０部２
−ヒドロキシエチルメタクリレート １５＃ビニ
ルピロリドン １４’メチ
ルメタクリレート ３０１ジ
メチルアミンアクリルアミド ９〃より
成る共重合体１６部に４．４′−ジアジドカルコン０．
６５部、Ｎｅｗｃｏｌ ７１０ （日本乳化剤（掬製、
非イオン界面活性剤）０．０８部、エチルセロノル１８
４部を混合溶解させた溶液を可染性感光性樹脂液とした
。(Example) Example 1゜Dimethylaminopropylacrylamide 30 parts 2
-Hydroxyethyl methacrylate 15# vinylpyrrolidone 14' methyl methacrylate 301 dimethylamine acrylamide 16 parts of a copolymer consisting of 9.4,4'-diazide chalcone 0.
65 parts, Newcol 710 (Nippon Emulsifier (Kiyomi),
Nonionic surfactant) 0.08 part, ethylcelonol 18
A solution obtained by mixing and dissolving 4 parts was used as a dyeable photosensitive resin liquid.
次にガラス基板にシランカップリング剤ＫＢＭ５０３（
信越化学工業■）１０％エタノール溶液を塗布し風乾後
１１０℃、５分間加熱乾燥したものを塗布用基材とした
。Next, silane coupling agent KBM503 (
Shin-Etsu Chemical Co., Ltd. ■) A 10% ethanol solution was applied, air-dried, and then heated at 110° C. for 5 minutes to prepare a coating substrate.
この塗布用基材表面にロールコータ−法により前記可染
性感光性樹脂液を塗布し、これを１００°Ｃ１３０分乾
燥後、解像度テスト用パターンを有するマスクを介して
面照度８ ｍＷ／ ｃｍ２のＵＶ照射を３０秒間行い、
エマルゲン９１３（花王石鹸■製、ポリオキシエチレン
ノニルフエノールエーテル型非イオン界面活性剤）を水
１０００部に対して２部、含有する６０℃の現像液にて
攪拌下、５分間現像を行うと照射部のみ可染膜を有する
ガラス基板が得られた。この可染性膜は０．７μの膜厚
であった。The dyeable photosensitive resin liquid was applied to the surface of this coating base material by a roll coater method, and after drying at 100°C for 130 minutes, it was exposed to a surface illuminance of 8 mW/cm2 through a mask having a resolution test pattern. UV irradiation is performed for 30 seconds,
After developing for 5 minutes with stirring in a developer solution at 60°C containing Emulgen 913 (manufactured by Kao Soap ■, polyoxyethylene nonylphenol ether type nonionic surfactant) at 2 parts per 1000 parts of water, irradiation was performed. A glass substrate was obtained which had a dyeable film only on a portion thereof. This dyeable film had a thickness of 0.7μ.
このガラス基板を１５０℃、３０分間乾燥後レッド２１
ＰＣ日本ｆヒ薬■製、カラーフィルター用色素）を０２
％となるように水に溶解させ６０°Ｃ１１０分間染色を
行うと濃厚赤色のパターンに染色されたガラス板が得ら
れた。After drying this glass substrate at 150°C for 30 minutes, Red 21
PC Nippon fhiyaku ■, color filter dye) 02
% in water and dyed at 60°C for 110 minutes, a glass plate dyed in a deep red pattern was obtained.
この染色膜の解像度は８μであった。The resolution of this stained membrane was 8μ.
参考例１゜
実施例１に於いてＮｅｗｃｏｌ ７１０を含まない可染
性感光性樹脂液を用いて同様の操作を行った所、染色膜
の解像度は２０μであった。Reference Example 1 When the same operation as in Example 1 was carried out using a dyeable photosensitive resin solution not containing Newcol 710, the resolution of the dyed film was 20μ.
実施例２゜
ジメチルアミノプロピルアクリルアミド ３１部２
−ヒドロキシエチルメタクリレート １６’ビニ
ルピロリドン １６１メ
チルメタクリレート １４’
メチルアクリレート １５部
ジメチルアミンアクリルアミド ９Ｉ
より成る共重合体１５部に４，４′−ジアジドカル−１
７０，６部、Ｎｅｗｃｏｌ ７１４ （日本乳化剤■製
、非イオン界面活性剤）０．３部、エチルセロソルブ８
５部を混合溶解させたｍ液を可染性感光性樹脂液とした
。Example 2゜Dimethylaminopropylacrylamide 31 parts 2
-Hydroxyethyl methacrylate 16' Vinylpyrrolidone 161 Methyl methacrylate 14'
Methyl acrylate 15 parts Dimethylamine acrylamide 9I
4,4'-diazidecal-1 to 15 parts of a copolymer consisting of
70.6 parts, Newcol 714 (manufactured by Nippon Nyukazai ■, nonionic surfactant) 0.3 parts, ethyl cellosolve 8
A dyeable photosensitive resin solution was prepared by mixing and dissolving 5 parts of the m solution.
この可染性感光性樹脂液を実施例１と同様の操作により
ガラス板に塗布、乾燥、解像度テスト用パターンを有す
るマスクを介してのＵＶ照射、エマルゲン９１３を含む
現像液による現像、１５０℃、３０分間の後乾燥を行っ
た。この可染性膜の膜厚は０．５μであった。This dyeable photosensitive resin liquid was applied to a glass plate in the same manner as in Example 1, dried, UV irradiated through a mask having a resolution test pattern, developed with a developer containing Emulgen 913, 150°C, Post-drying was carried out for 30 minutes. The thickness of this dyeable film was 0.5μ.
このガラス板をグリーンＩＰ（日本化薬■製、カラーフ
ィルター用色素）を０．１２％となるように水に溶解さ
せ、６２℃、１１分間染色を行うと濃厚緑色のパターン
に染色されたガラス板が得られた。このガラス板染色膜
の解像度は７μであった。When this glass plate was dyed with 0.12% Green IP (manufactured by Nippon Kayaku ■, color filter dye) in water and dyed at 62°C for 11 minutes, the glass was dyed in a deep green pattern. A board was obtained. The resolution of this glass plate dyed film was 7μ.
参考例２゜
実施例２に於いてＮｅｗｃｏｌ ７１４を含まない可染
性感光性樹脂液を用いて同様の操作を行った所、染色膜
の解像度は２５μであった。Reference Example 2 When the same operation as in Example 2 was carried out using a dyeable photosensitive resin solution not containing Newcol 714, the resolution of the dyed film was 25μ.
（発明の効果）
本発明は可染性感光性樹脂組成物を用いて基材表面に皮
膜を設けマスクを介して露光し、現像液にて現像する事
に於いて、可染性感光性樹脂組成物にあらかじめ非イオ
ン界面活性剤を含法を用いると高解像度のパターンを有
する高品質のものが得られると共に収率の向上に役立つ
。(Effects of the Invention) The present invention provides a dyeable photosensitive resin composition in which a film is formed on the surface of a substrate using a dyeable photosensitive resin composition, exposed to light through a mask, and developed with a developer. When a nonionic surfactant is added to the composition in advance, a high-quality product with a high-resolution pattern can be obtained and the yield can be improved.
従って本性は色分解用フィルターの品質向上が計れる上
に、収率の向上によりコストダウンにも役立つ。Therefore, this property can not only improve the quality of color separation filters, but also help reduce costs by improving yield.
Claims (1)
水性モノマー（Ｃ） より成る共重合体（Ｄ） を構成成分とする可染性感光性樹脂組成物を用いて基材
表面に皮膜を設けマスクを介して露光し、現像液にて現
像する際に、可染性感光性樹脂組成物に予め非イオン界
面活性剤を含有させる事を特徴とする可染性樹脂膜のパ
ターン形成法。[Claims] A copolymer (D) consisting of a) a dyeable monomer (A), b) a hydrophilic monomer other than the dyeable monomer (B), and c) a hydrophobic monomer (C). When forming a film on the surface of a substrate using a dyeable photosensitive resin composition, exposing it to light through a mask, and developing it with a developer, a nonionic surfactant is added to the dyeable photosensitive resin composition in advance. A pattern forming method for a dyeable resin film characterized by containing the dyeable resin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62051882A JPS63218957A (en) | 1987-03-09 | 1987-03-09 | Method for forming pattern of dyeable resin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62051882A JPS63218957A (en) | 1987-03-09 | 1987-03-09 | Method for forming pattern of dyeable resin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63218957A true JPS63218957A (en) | 1988-09-12 |
Family
ID=12899251
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62051882A Pending JPS63218957A (en) | 1987-03-09 | 1987-03-09 | Method for forming pattern of dyeable resin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63218957A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02239205A (en) * | 1989-03-13 | 1990-09-21 | Hitachi Chem Co Ltd | Production of color filter |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5660441A (en) * | 1979-10-22 | 1981-05-25 | Asahi Chem Ind Co Ltd | Photosensitive resin composition improved in water development property and manufacture of photosensitive resin plate using this composition |
| JPS57178242A (en) * | 1981-04-27 | 1982-11-02 | Konishiroku Photo Ind Co Ltd | Photosensitive lithographic plate |
| JPS6079349A (en) * | 1983-10-06 | 1985-05-07 | Mitsubishi Chem Ind Ltd | Water-soluble photosensitive composition and organic color filter |
| JPS6236657A (en) * | 1985-08-10 | 1987-02-17 | Japan Synthetic Rubber Co Ltd | Resist composition |
| JPS62226143A (en) * | 1986-03-27 | 1987-10-05 | Fuji Photo Film Co Ltd | Photosensitive composition |
-
1987
- 1987-03-09 JP JP62051882A patent/JPS63218957A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5660441A (en) * | 1979-10-22 | 1981-05-25 | Asahi Chem Ind Co Ltd | Photosensitive resin composition improved in water development property and manufacture of photosensitive resin plate using this composition |
| JPS57178242A (en) * | 1981-04-27 | 1982-11-02 | Konishiroku Photo Ind Co Ltd | Photosensitive lithographic plate |
| JPS6079349A (en) * | 1983-10-06 | 1985-05-07 | Mitsubishi Chem Ind Ltd | Water-soluble photosensitive composition and organic color filter |
| JPS6236657A (en) * | 1985-08-10 | 1987-02-17 | Japan Synthetic Rubber Co Ltd | Resist composition |
| JPS62226143A (en) * | 1986-03-27 | 1987-10-05 | Fuji Photo Film Co Ltd | Photosensitive composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02239205A (en) * | 1989-03-13 | 1990-09-21 | Hitachi Chem Co Ltd | Production of color filter |
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