WO2001095033A1 - Photosensitive resin composition and photosensitive material using the same - Google Patents
Photosensitive resin composition and photosensitive material using the same Download PDFInfo
- Publication number
- WO2001095033A1 WO2001095033A1 PCT/JP2001/004748 JP0104748W WO0195033A1 WO 2001095033 A1 WO2001095033 A1 WO 2001095033A1 JP 0104748 W JP0104748 W JP 0104748W WO 0195033 A1 WO0195033 A1 WO 0195033A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- compound
- photosensitive
- resin composition
- photosensitive material
- present
- Prior art date
Links
- 0 COC1=CC=CC*1 Chemical compound COC1=CC=CC*1 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
- G03F7/027—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
-
- 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
Definitions
- the present invention relates to a highly sensitive photosensitive material used for manufacturing print circuit boards, developing a high productivity, and to a photosensitive resin composition used therein.
- photosensitive material such as a dry film resist or the like are generally used.
- the photosensitive materials are required to become proportionately sensitive, so as to provide a higher resolution. It has been reported (U.S. Patent No.
- hexaarylbisimidazole (hereinafter referred to as '"HABI") which is of the same type of compound with B-CIM is also commercially used in manufacturing dry film resists .
- the present invention provides a photosensitive resin composition
- a photosensitive resin composition comprising (A) a binder polymer having a carboxyl group, (B) a photopolymerizable compound having an ethylenic unsaturated group, and (C) a photoinitiator compound identified as Compound (1) , as a photoinitiator, and also provides a photosensitive material characterized by the use of such a photosensitive resin composition.
- Fig. 1 illustrates a UN ray-absorption spectrum of the compound prepared in Example 1 of the present invention.
- the photoinitiator compound of the present invention is highly soluble in a resin composition and, therefore, hardly forms a particulate matter, which tends to deposit on the resist substrate, and yet has a higher sensitivity, as compared with conventional B-CIM.
- examples of (B) a compound having a polymerizable ethylenic unsaturated group include a vinyl monomer or the like.
- examples of a monofunctional vinyl monomer include monoacrylate or monomethacrylate
- examples of a difunctional vinyl monomer include diacrylate or dimethacrylate
- examples of a polyfunctional vinyl monomer include compounds obtained by reacting an a , ⁇ -unsaturated carboxylic acid with a polyhydric alcohol or a glycidyl group-containing compound.
- a blending amount of the component (A) is preferably 0.6 to 4 times the amount by weight of the component (B) .
- a blending amount of the photoinitiator compound (C) is preferably 0.005 to 0.15 time the amount by weight of the total weight of the component (A) and the component (B) .
- the photosensitive resin composition of the present invention may further contain an N,N' -tetraalkyl-4, 4 ' - dia inobenzophenone such as N,N' -tetraethyl-4 , 4 ' - diaminobenzophenone, an N-aryl- -amino acid such as N- phenylglycine, or the like as an additive, and may further contain a heat polymerization inhibitor, an adhesiveness-imparting agent, a colorant or the like, if necessary.
- the photosensitive material of the present invention is prepared by coating a solution of the photosensitive resin composition of the present invention as a liquid resist on the surface of a metal as a substrate, and by drying the coated layer to form a photosensitive layer.
- a print circuit board can be produced by printing a device pattern on the photosensitive material by means of lithography technique and, then, processing by etching, plating or the like.
- the photosensitive material of the present invention may be produced by coating the solution of the photosensitive resin composition of the present invention on a polymeric film such as polyethylene terephthalate by a well known method, drying to form a dry film and, then, laminating the dry film on the surface of a metal as a substrate to form a photosensitive layer.
- the photosensitive resin composition of the present invention may be diluted with a solvent such as acetone, methyl cellosolve, methyl ethyl ketone, toluene, methanol, propylene glycol monoethyl ether, dimethylformamide or the like, or a mixture solvent thereof.
- a solvent such as acetone, methyl cellosolve, methyl ethyl ketone, toluene, methanol, propylene glycol monoethyl ether, dimethylformamide or the like, or a mixture solvent thereof.
- the coating can be carried out with a roll coater, an air knife coater, a bar coater, a spin coater or the like.
- the drying is carried out at a temperature of 60 to 130°C.
- the photosensitive layer preferably has a thickness of 5 to 100 ⁇ m.
- Light exposure of the photosensitive layer is carried out by light generated from a light source such as a high pressure mercury lamp.
- Development of the exposed photosensitive layer is carried out by using an alkaline aqueous solution of sodium carbonate or other water-soluble alkaline materials.
- Etching and plating can be carried out by the conventional methods.
- the subsequent step of removing the light-cured part of the photosensitive layer can be carried out by using a strong alkaline aqueous solution.
- the maximum absorption wavelength of the UN ray- absorption spectrum was 234 nm. This compound provided a pale greenish radical coloration as irradiated to ultraviolet rays.
- Methacrylic acid, ethyl methacrylate and styrene were copolymerized to produce a carboxyl group-containing copolymer material having a molecular weight of 60,000. Having 100 g of this copolymer as the Component (A) , the Component (B) and the solvents were blended therewith as shown in the following Table 1, to obtain a solution of a photosensitive resin composition.
- Table 1 Table 1
- a Stoufer 21 gradation step tablet (manufactured by Electrophotographic Association) was placed as a negative on the above produced photosensitive material, and a quartz glass plate (manufactured by Seiko Tokushu Glass K.K.) of 2.3 mm in thickness was further placed thereon and was further suction-adhered under vacuum to completely adhere the negative and the photosensitive material, which were then exposed to light from a parallel light-exposing apparatus (manufactured by Ushio Inc.) having a high pressure mercury lamp at 600 i /cm .
- the photosensitive material was dipped and shaken in 500 cc of a 1% sodium carbonate aqueous solution at 20°C for 90 seconds, and consequently the unexposed part could be easily dissolved and removed.
- the thickness of the light-cured layer formed on the coated substrate was measured with a contact type film thickness measuring apparatus (manufactured by Tokyo Seimitsu Co., Ltd.).
- a photosensitive resin composition containing B-CIM was prepared in the same manner as above, and the photosensitive resin composition was coated on a substrate in the same manner as above to form a light- cured layer which was then subjected to the same measurement as mentioned above.
- the layer's thickness of each step of the gradation step tablet was measured, and the highest step number of the gradation step tablet retaining at least 50% of the maximum layer thickness was made as an index for a sensitivity, as shown in the following Table 2.
- Table 2 Table 2
- Photosensitive resin compositions were prepared by using 5.0 g of the photoinitiator compound of the present invention (Example 2) and 5.0 g of B-CIM (manufactured by Hodogaya Chemical Co., Ltd.) (Comparative Example 1), respectively, in the same manner as in Example 1.
- the photoinitiator compound of the present invention was easily dissolved, but it was necessary for dissolving B- CIM to stir for 30 minutes.
- Each of the photosensitive resin compositions thus prepared was coated on a total of 44 sheets of slide glass (manufactured by Matsunami Glass Kogyo K.K.) with a bar coater in such an amount as to provide a dry solid content of 0.1 g per sheet, and was dried in an oven at 110°C for 10 minutes to form a photosensitive layer.
- a developing solution was prepared in two 200 ml beakers, by putting 150 ml of a 1% sodium carbonate aqueous solution in each of the beakers placed in a water bath controlled at 40°C, stirring by means of a compressed air blown therein and maintaining the temperature at 40°C.
- Each of the developing solutions became a cloudy suspension.
- the cloudy suspension was allowed to stand at room temperature for 3 days and was then decanted to recognize a white precipitate at the bottom of the beaker containing each of the developing solutions.
- the precipitate was dispersed in 3 ml of distilled water added, and the dispersion was decanted, thereby removing the white matter, but fine sand-like particulate matter was still deposited on the bottom of each beaker.
- the amount of the deposited matter in each beaker was visually compared, and it was observed that an amount of the deposited matter in the beaker containing the photoinitiator compound of the present invention was notably smaller than that in the beaker containing B-CIM.
- the photosensitive resin composition of the present invention hardly forms a particulate matter in a developing solution, and yet has a high sensitivity.
- the photosensitive material of the present invention does not cause a disconnected circuit, a short circuit or the like due to the particulate matter formed in a developing solution in manufacturing print circuit boards, and provides a satisfactory resist pattern with a satisfactory operation efficiency.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2001260720A AU2001260720A1 (en) | 2000-06-06 | 2001-06-05 | Photosensitive resin composition and photosensitive material using the same |
EP01934553A EP1290499A1 (en) | 2000-06-06 | 2001-06-05 | Photosensitive resin composition and photosensitive material using the same |
JP2002502522A JP2003536104A (en) | 2000-06-06 | 2001-06-05 | Photosensitive resin composition and photosensitive material using the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000168721 | 2000-06-06 | ||
JP2000-168721 | 2000-06-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001095033A1 true WO2001095033A1 (en) | 2001-12-13 |
Family
ID=18671688
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2001/004748 WO2001095033A1 (en) | 2000-06-06 | 2001-06-05 | Photosensitive resin composition and photosensitive material using the same |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1290499A1 (en) |
JP (1) | JP2003536104A (en) |
AU (1) | AU2001260720A1 (en) |
WO (1) | WO2001095033A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5765001B2 (en) * | 2011-03-28 | 2015-08-19 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element using the same, method for producing resist pattern, and method for producing printed wiring board |
CN111258180B (en) * | 2018-11-30 | 2024-03-08 | 常州正洁智造科技有限公司 | Hexaarylbisimidazoles mixed photoinitiator and application thereof |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3479185A (en) * | 1965-06-03 | 1969-11-18 | Du Pont | Photopolymerizable compositions and layers containing 2,4,5-triphenylimidazoyl dimers |
EP0352503A1 (en) * | 1988-07-20 | 1990-01-31 | BASF Aktiengesellschaft | Light-sensitive negatively acting recording layer |
EP0355335A1 (en) * | 1988-07-20 | 1990-02-28 | BASF Aktiengesellschaft | Light-sensitive recording material, its use and leuco compound suitable therefor |
EP0388875A2 (en) * | 1989-03-21 | 1990-09-26 | BASF Aktiengesellschaft | Light sensitive preparation, and process for the fabrication of photoresistors and printing plates |
EP0414100A2 (en) * | 1989-08-22 | 1991-02-27 | BASF Aktiengesellschaft | Photosensitive positive working mixture |
JPH04164902A (en) * | 1990-10-30 | 1992-06-10 | Nippon Kayaku Co Ltd | Photopolymerizable composition for color filter |
JPH05333541A (en) * | 1992-06-03 | 1993-12-17 | Nippon Kayaku Co Ltd | Photopolymerizable composition for color filter and color filter |
-
2001
- 2001-06-05 EP EP01934553A patent/EP1290499A1/en not_active Withdrawn
- 2001-06-05 WO PCT/JP2001/004748 patent/WO2001095033A1/en not_active Application Discontinuation
- 2001-06-05 JP JP2002502522A patent/JP2003536104A/en not_active Withdrawn
- 2001-06-05 AU AU2001260720A patent/AU2001260720A1/en not_active Abandoned
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3479185A (en) * | 1965-06-03 | 1969-11-18 | Du Pont | Photopolymerizable compositions and layers containing 2,4,5-triphenylimidazoyl dimers |
EP0352503A1 (en) * | 1988-07-20 | 1990-01-31 | BASF Aktiengesellschaft | Light-sensitive negatively acting recording layer |
EP0355335A1 (en) * | 1988-07-20 | 1990-02-28 | BASF Aktiengesellschaft | Light-sensitive recording material, its use and leuco compound suitable therefor |
EP0388875A2 (en) * | 1989-03-21 | 1990-09-26 | BASF Aktiengesellschaft | Light sensitive preparation, and process for the fabrication of photoresistors and printing plates |
EP0414100A2 (en) * | 1989-08-22 | 1991-02-27 | BASF Aktiengesellschaft | Photosensitive positive working mixture |
JPH04164902A (en) * | 1990-10-30 | 1992-06-10 | Nippon Kayaku Co Ltd | Photopolymerizable composition for color filter |
JPH05333541A (en) * | 1992-06-03 | 1993-12-17 | Nippon Kayaku Co Ltd | Photopolymerizable composition for color filter and color filter |
Non-Patent Citations (2)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 016, no. 466 (C - 0989) 28 September 1992 (1992-09-28) * |
PATENT ABSTRACTS OF JAPAN vol. 018, no. 166 (P - 1713) 18 March 1994 (1994-03-18) * |
Also Published As
Publication number | Publication date |
---|---|
AU2001260720A1 (en) | 2001-12-17 |
JP2003536104A (en) | 2003-12-02 |
EP1290499A1 (en) | 2003-03-12 |
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