GB1575281A - Positive working photosensitive elements - Google Patents
Positive working photosensitive elements Download PDFInfo
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- GB1575281A GB1575281A GB1596478A GB1596478A GB1575281A GB 1575281 A GB1575281 A GB 1575281A GB 1596478 A GB1596478 A GB 1596478A GB 1596478 A GB1596478 A GB 1596478A GB 1575281 A GB1575281 A GB 1575281A
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
- Materials For Photolithography (AREA)
- Hydrogenated Pyridines (AREA)
Description
(54) POSITIVE WORKING PHOTOSENSITIVE ELEMENTS
(71) We, E. I. DU PONT DE NEMOURS AND COMPANY, a
Corporation organised and existing under the laws of the State of Delaware, United
States of America, located at Wilmington, State of Delaware, United States of
America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to new photosensitive elements, and pertains more particularly to positive-working photosensitive elements.
Photosensitive compositions which change their solubility under the influence of actinic radiation are known in image reproduction technology. A negative or positive image is formed depending, respectively, on whether the solubility of the composition in a suitable solvent is decreased or increased on exposure.
Compositions which yield negative images of the original are much more common than compositions which yield positive images.
One positive-working system is based on the photodecomposition of o- quinone diazides. The photodecomposition products occurring therein are more soluble in aqueous alkali than are the starting compounds. Another positiveworking system is disclosed dn U.S. Patent 3,782,951 which describes a composition of a hexaaryldiimidazole, a hydrogen donor, an ethylenically unsaturated compound, and an organic polymeric binder.
Still another positive-working composition is known from German OS 2,242,106. This composition contains a l,4-dihydro-4-(2'-nitrophenyl)-pyridine as the light-sensitive compound, and excels primarily in having a comparatively high light-sensitivity, and in requiring relatively simple processing. A disadvantage with this composition, however, is that the available solubility difference between exposed and unexposed image areas is not large enough for many practical applications. As a result of this small solubility difference, during the development process the unexposed areas will begin dissolving away before relief image formation is complete, thus leading to poorly formed relief, thin layers, and decreased image sharpness. These deficiencies can be very disadvantageous in various applications. Should the material, for example, be used for the preparation of printed circuits, then the light-sensitive layer remaining on the support after the development will start to dissolve and will be so thin that it no longer fully fulfills its purpose as a resist pattern. As a result there will be faulty etchings which impair the quality of the desired printed circuits. Should the layers be used for the preparation of offset plates, there will be no mechanical capacity to withstand the stress which such plates undergo.
A substantial difference in the solubility of exposed and unexposed image areas, i.e., a wide processing latitude, thus is an essential requirement which must be fulfilled by a photosensitive stratum processed by the development procedure.
In accordance with this invention there is provided a positive working photosensitive element which comprises a support bearing a photosensitive layer comprising at least one polymeric binder and a dihydropyridine compound of the formula:
wherein
R1 and R2 are alkyl, aryl, substituted aryl or a heterocyclic ring,
R3 and R4 are COOR', COR' or CN, wherein R' is alkyl, substituted alkyl, or aryl, or
R, and R3 and/or R2 and R4 when taken together with the carbon atoms to which they are attached form a 5- or 6-membered carbocyclic or heterocyclic ring.
Compounds of the invention are summarized in the following Table. In R1 and
R2 alkyl can be of 1 to 20 carbon atoms, aryl can be of 6 to 10 carbon atoms and substituted aryl can be of 6 to 14 carbon atoms; in R3 and R4, R' can be alkyl of 1 to 4 carbon atoms, substituted alkyl of 1 to 4 carbon atoms or aryl of 6 to 10 carbon atoms.
TABLE
Compound No. R, R3 1 -CH3 -COOCH, 2 -CH -COCH3 3 -CH3 -COOC(CH3)3 4 -CH3 -COOC,H, 5 -C17H35 COOC2Hs 6 EPOCH3 -COOC2H6 7 tNO2 -C00C2Hs g -C4H9 -C0OC2H 9 -CH3 -CN 10 -CH3 -COOC,H, 11 -CH3 COOC2Hs 12 -CH2 COOC2Hs 13 CH2C(CH3)2-CH2-C 14 CH2-CH2-CH2-C=0 TABLE
Compound No. R2 R4 1 -CH -COOCH, 2 -CH3 -COCH3 3 -CH3 COOC(CH3)3 4. -CH3 -COOC2H 5 C"H3s COOC2Hs 6 0CH3 -COOC,H, 7 3No2 -COOC2Hs 8 -C4H9 -COOC2H5 9 -CH3 -CN 10 11 gs COCF3 12 CH2-CH2-CH2-C=O 13 CH2-C(CH3)2-CH2-C=O 14 CH2-CH2-CH2 C.=O The 1,4-dihydro-4-(5'-nitro-2'-furyl)-pyridines can be prepared according to the Hantzsch pyridine synthesis from 5-nitrofurfural, a p-ketocarboxylic acid ester or a ,B-ketocarboxylic acid nitrile or a p-diketone and ammonia or a ,B- aminocrotonic acid ester (Elderfield, Heterocycl. Compounds, Vol. 1, 1950, p. 462 ff).
The synthesis of 1 ,4.dihydro-2,6-dimethyl-4-(5'-nitro-2'-furyl)-pyridine-3,5-di- carboxylic acid-di-tert.-butyl ester (compound 3 of the Table) is described as follows, other compounds being prepared analogously to this.
A solution of 24.4 g 5-nitrofurfural diacetate; 33.2 g acetoacetic acid-tert.butyl ester; 5.0 g ammonium acetate; and 5.0 ml ammonia solution (25%) is heated for 6 hours in 40 ml pyridine on a vapor bath. After cooling, the solution is poured into 1 liter of ice water, and is allowed to stand overnight at OOC. The separated precipitate is recrystallized 4 times from hot ethanol. 12 g of yellow needles are obtained having a melting point of 195"C.
To prepare the photosensitive recording elements, the l,4-dihydro-4-(5'-nitro- 2'-furyl)-pyridines with at least a known compatible organic polymeric binder, e.g.
alkali soluble, are applied to a support, e.g. a film base according to a conventional coating process, e.g. dip coating, spin coating, coating with a doctor knife or spraying. A large number of binders, e.g. alkali-soluble binders, are known which are suitable for the named purpose of application. These binders frequently contain alkali-soluble promoting groups, such as acid anhydride, carboxyl- or sulfonic acid groups. As examples are named: acrylic acid and/or methacrylic acid polymers and/or their copolymers with other suitable monomers, e.g. acrylic acid esters or other acryl derivatives, vinyl compounds, such as vinyl ether, vinyl acetate or their saponification products, styrene, vinyl pyrrolidone, butadiene and related monomers; polyacrylic acid anhydrides, copolymers of maleic acid anhydride, maleic acid, maleic acid monoesters, -monoamides and/or anhydrides and derivatives of related compounds, e.g. itaconic acid, with suitable comonomers, e.g. styrene, ethylene, vinyl ethers or vinyl acetates, polystyrene sulfonic acid and/or their copolymers; cellulose derivatives, such as, e.g. carboxymethyl cellulose, cellulose phthalate or -succinate, alginic acid and their derivatives.
Additionally, phenol-formaldehyde resins known under the designation of "Novolac" (Registered Trade Mark) are suitable.
Copolymers of maleic acid anhydride and styrene are especially advantageous polymeric binders for the preparation of elements according to the invention. The concentration of 1,4-dihydro-4(5'-nitro-2'-furyl)-pyridines preferably is 20 to 80% by weight based on the total weight of the photosensitive composition. The photosensitive compounds can be used alone or in mixtures with one another. The concentration of the polymeric binder preferably is 20 to 80% by weight based on the total weight of the composition.
By the addition ofan initiator or initiator system, the sensitivity of the layer can be improved. Suitable initiators are known from the literature, e.g.
benzophenone, Michler's ketone or hexaaryl bisimidazoles. Michler's ketone, pdimethylaminobenzaldehyde, 5-nitroindazole, and nitroaniline have proved effective. The photosensitive layer can also contain suitable dyes and pigments as well as other additives, such as plasticizers, adhesives promoters, etc. The initiator or initiator system, if present, can be used in amounts up to 10% by weight based on the total composition weight.
As supports, one may use film bases customarily employed for the manufacture of photographic elements. Suitable supports are: paper, coated paper, foils and sheets of metal such as aluminum and copper, supports of synthetic polymeric materials such as polyethylene, polypropylene, polyesters, e.g.
polyethylene terephthalate, and polyamides, as well as supports of cellulose acetate, cellulose butyrate, and cellulose acetatebutyrate. The photosensitive layer can be applied directly onto one of these supports and used in this form to prepare the relief image. It can also be first coated onto a temporary strippable support, preferably a transparent plastic film, and then transferred by lamination onto the support with which it will be used. The thickness of the photosensitive layer can be from 10 to 150 m or more.
The recording element can contain conventional intermediate layers, e.g. to anchor the photosensitive layer to its support. Dyes or pigments can be present in the support or in the intermediate layers.
To prepare the images, the photosensitive element is exposed imagewise by radiation sources which emit radiation rich in ultraviolet light, e.g. mercury vapor lamps and Xenon lamps. The element is then developed by washing out the exposed image portions. Preferably, for washout aqueous alkali solutions are used which can contain as suitable alkali, e.g. alkali carbonates, borates and alkali hydroxides, as well as the known carbonate-, borate- and phosphate-buffer systems. The washout solutions, moreover, can contain surface-active substances.
Depending on the polymeric binder used, naturally, organic solvents can also be used for washout.
It is completely surprising and not obvious for those skilled in the art that the described 1 ,4-dihydro-4.(5'-nitro-2'-furyl).pyridines are photosensitive compounds having such good properties. It is known from literature (J. Am. Chem. Soc.
7a1955, p. 447, lines 1--3 right column and remark 3), that photosensitivity is a function of the position of the nitro group in the molecule. Thus, the 1 ,4-dihydro-4- (2'-nitrophenyl)-pyridines of German OS 2,242,106 are described as photosensitive compounds, while the corresponding 3'- or 4'-nitro-derivatives, where the nitro group is not in the o-position for linking, are insensitive to light. Therefore, based on the position of the nitro group in the molecule, it is unexpected by those skilled in the art that the l,4-dihydro-4-(5'-nitro-2'.furyl)-pyridines are photosensitive. lt is also unexpected that photosensitive layers prepared from these compounds are superior to the compounds disclosed in German OS 2,242,106.
The best method of carrying out the invention is illustrated in Example 4 wherein an offset printing plate is prepared using Compound 3 of the Table, 1,4 dihydro-2,6-dimethyl-4.(5'-nitro-2'-furyl)pyridine.3,5-dicarboxylic acid-di-tert.butyl ester, and an alkali-soluble organic polymeric binder, a copolymer of styrene and maleic acid anhydride.
The photosensitive elements of the invention are especially suited for the preparation of printing plates, particularly offset printing plates, as well as in the preparation of printed circuits using an element having a strippable support.
Transparent or opaque positive copies of line, screen, or halftone originals can also be prepared.
EXAMPLES
The following examples illustrate the invention wherein the percentages are by weight except where noted.
EXAMPLE 1.
A casting solution of the following composition is applied to an aluminum plate, as it is used for the preparation of offset printing plates:
10.0 g phenol formaldehyde resin
("Alnovol") (Registered Trade Mark)
5.0 ml glycol monomethyl ether
0.1 g of a blue triaryl methane dye
("Victoria Pure Blue FGA")
2.5 g Compound 1 of Table
0.25 g p-dimethyl aminobenzaldehyde 90.0 ml acetone
The thickness of the dried layer is 20 ,um.
The plate is then exposed under an original for 120 seconds at a distance of 60 cm using a mercury vapor lamp (1,000W). The exposed image portions are then subsequently washed out using an aqueous solution of the following composition:
30 g Na2CO3 Anh.
30 g Na3PO4. 12 H2O 25 ml NaOH (10%) Water to 1 liter.
A positive-working offset printing plate of high life expectancy is obtained.
EXAMPLE 2.
A photosensitive mixture of the following composition is applied to a polyethylene terephthalate film base, is dried, and is provided with a transparent removable cover film:
10.0 g copolymer of methyl methacrylate (40 Mol %)/ethyl acrylate
(55 Mol %) and acrylic acid (5 Mol %)
5.0 g Compound 14 of Table
0.1 g of a mixture of triethylene glycol-di-n-hexanoic acid ester and
triethylene glycol-di-n-octanoic acid ester (ratio 1:1)
0.1 g of a blue triaryl methane dye ("Victoria Pure Blue FGA")
dissolved in 100 ml methylene chloride.
The coating thickness of the photosensitive layer after drying is 50 4m.
After the removal of the cover film the photosensitive layer is laminated onto a copper circuit board to form a photoresist as it is used for the preparation of printed circuits, and is exposed under an original for 240 seconds using a mercury vapor lamp (1,000W) at a distance of 60 cm. Development takes place using a solution of the following composition:
20 g Na3PO4.l2 H2O 20 ml methyl glycol
1 liter water.
The plate is then etched in conventional manner using a ferric chloride solution. After removal of the photoresist film a printed circuit of high quality is obtained.
EXAMPLE 3.
The casting solution A of the following composition is prepared:
9.0 g phenol formaldehyde resin ("Alnovol")
4.5 g Compound 4 of Table
0.1 g of a mixture of triethylene glycol-di-n-hexanoic acid ester and
triethylene glycol-di-n-octanoic acid ester as in Example 2
0.1 g of a blue triaryl methane dye ("Victoria Pure Blue FGA")
150.0 g acetone
20.0 g ethylene glycol monoethyl ester
A second casting solution B is prepared, which differs from solution A only in that it contains 4.5 g of Compound 2) of German OS 2,242,106 as the photosensitive compound.
Both casting solutions are applied to aluminum plates as they are used for the preparation of offset printing forms, to provide a coating thickness after drying of 20 ,um. The elements formed are exposed as described in Example 1, and the exposed areas are washed out with a solution of the following composition:
20 g Na2CO3
20 g Na3PO4. 12 H2O
3.3 g NaOH
20 ml glycol monoethyl ether
Water to 1 liter.
The following results are obtained:
Plate A Plate B
Start of image formation 20 seconds 50 seconds
Completion of image
formation 50 seconds 120 seconds
Dissolution of the
layer 150 seconds 150 seconds
As clearly seen from the results above, Plate A excels Plate B by a considerably wider processing latitude.
EXAMPLE 4.
A casting solution of the following photosensitive composition is applied to an aluminum plate, as it is used for the preparation of offset printing plates:
5.0 g copolymer of styrene (50 Mol %) and maleic acid anhydride
(50 Mol %)
2.5 g Compound 3 of Table
100.0 ml acetic acid ethyl ester.
The coating thickness of the dried coating is 20 ,um. The element is exposed as described in Example 2. The exposed image portions are subsequently dissolved out using a solution of the following composition:
20 g Na2CO3
20 g Na3PO4. 12 H2O 3 g NaOH
20 ml glycol monoethyl ether
Water to I liter.
The following results are obtained:
Start of image recording: 20 seconds
Completion of image recording: 50 seconds
Dissolution of the layer: 200 seconds
EXAMPLE 5.
A casting solution of the following composition is applied to a polyethylene terephthalate film base, the dry coating thickness of the cast coating is 10 ,um: 5.0 g copolymer of styrene and maleic acid monoester
3.0 g Compound 2 of Table
0.5 g of a red disazo dye, Ceres RedB 100.0 ml methylene chloride
After drying, the layer is exposed for 120 seconds at a distance of 60 cm using an ultraviolet lamp (1,000W). The exposed layer portions are subsequently dissolved out using a solution of the following composition:
20 g Na3PO4 12 H2O 20 ml methyl glycol
Water to I liter.
A red duplicate of the original on a transparent support is obtained.
EXAMPLE 6.
Onto a polyethylene terephthalate film base is applied a cast solution of the following composition which is then dried:
10.0 g of a mixture of a copolymer of methyl methacrylate (40 Mol%),
ethyl acrylate (55 Mol%), and acrylic acid (5 Mol%) and carbon
black in the ratio 1:1
0.5 ml of a mixture of triethylene glycol-di-n-hexanoic acid ester and tri
ethylene glycol-di-n-octanoic acid ester as in Example 2
90.0 ml acetone
An additional layer of the following composition is then applied onto this layer:
10.0 g of a copolymer of styrene (50 Mol%) and maleic acid anhydride
(50 Mol%)
2.5 g Compound 3 of Table
2.5 ml triethylene glycol-di-n-hexanoic acid ester and triethylene glycol
di-n-octanoic acid ester as in Example 2
100.0 ml acetic acid ethyl ester
After drying the element is exposed for 2 minutes using an ultraviolet lamp (1,000W) through a screen original.
After washing out the exposed points using a solution of the following composition:
20 g Na3PO4.l2 H2O 20 ml methyl glycol
Water to 1 liter a positive screen image is obtained.
WHAT WE CLAIM IS:
1. A positive working photosensitive element, which element comprises a support bearing a photosensitive layer comprising at least one organic polymeric binder and a dihydropyridine compound of the formula
wherein R, and R2 are alkyl, aryl, substituted aryl or a heterocyclic ring,
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (8)
- **WARNING** start of CLMS field may overlap end of DESC **.After drying, the layer is exposed for 120 seconds at a distance of 60 cm using an ultraviolet lamp (1,000W). The exposed layer portions are subsequently dissolved out using a solution of the following composition:20 g Na3PO4 12 H2O20 ml methyl glycol Water to I liter.A red duplicate of the original on a transparent support is obtained.EXAMPLE 6.Onto a polyethylene terephthalate film base is applied a cast solution of the following composition which is then dried: 10.0 g of a mixture of a copolymer of methyl methacrylate (40 Mol%), ethyl acrylate (55 Mol%), and acrylic acid (5 Mol%) and carbon black in the ratio 1:1 0.5 ml of a mixture of triethylene glycol-di-n-hexanoic acid ester and tri ethylene glycol-di-n-octanoic acid ester as in Example 2 90.0 ml acetone An additional layer of the following composition is then applied onto this layer: 10.0 g of a copolymer of styrene (50 Mol%) and maleic acid anhydride (50 Mol%) 2.5 g Compound 3 of Table 2.5 ml triethylene glycol-di-n-hexanoic acid ester and triethylene glycol di-n-octanoic acid ester as in Example 2 100.0 ml acetic acid ethyl ester After drying the element is exposed for 2 minutes using an ultraviolet lamp (1,000W) through a screen original.After washing out the exposed points using a solution of the following composition:20 g Na3PO4.l2 H2O20 ml methyl glycol Water to 1 liter a positive screen image is obtained.WHAT WE CLAIM IS: 1. A positive working photosensitive element, which element comprises a support bearing a photosensitive layer comprising at least one organic polymeric binder and a dihydropyridine compound of the formulawherein R, and R2 are alkyl, aryl, substituted aryl or a heterocyclic ring,R3 and R4 are COOR', COR' or CN, where R' is alkyl, substituted alkyl or aryl, or R, and R3 and/or R2 and R4 when taken together with the carbon atoms to which they are attached form a 5- or 6-membered carbocyclic or heterocyclic ring.
- 2. An element according to claim 1 wherein the dihydropyridine compound is present in an amount of 20 to 80 percent by weight based on the total weight of the photosensitive layer.
- 3. An element according to claim 1 or 2 wherein an initiator is present in the photosensitive layer in an amount up to 10% by weight of the photosensitive layer.
- 4. An element according to claim 1, 2 or 3 wherein the dihydropyridine compound is I ,4-dihydro-2,6-dimethyl-4-(5'.nitro-2'-furyl)-3,5-diacetopyridine, 1,4 dihydro-2,6-dimethyl-4-(5'-nitro-2'-furyl)-pyridine-3,5-dicarboxylic acid-di-tert.butyl ester or 1 ,4-dihydro-2,6-dimethyl.4.(5'-nitro-2'.furyl)-pyridine-3,5-di.carboxylic acid diethyl ester.
- 5. An element according to claim 1, 2 or 3 wherein the dihydropyridine compound is 1 ,4-dihydro-2,6.dimethyl-4-(5'-nitro-2'-furyl)pyridine-3,5-dicarboxy- lic acid-di-tert.-butyl ester and the organic polymer binder is a copolymer of maleic acid anhydride and styrene.
- 6. An element according to claim 1 substantially as described in any one of the Examples.
- 7. A positive image formed by exposing imagewise to actinic radiation the photosensitive layer of an element as claimed in any one of the preceding claims and washing out the exposed areas of the layer.
- 8. A printed circuit formed by using a positive image as claimed in claim 7 as a photoresist when etching a circuit board in known manner.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772718130 DE2718130C2 (en) | 1977-04-23 | 1977-04-23 | photosensitive recording material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1575281A true GB1575281A (en) | 1980-09-17 |
Family
ID=6007089
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB1596478A Expired GB1575281A (en) | 1977-04-23 | 1978-04-21 | Positive working photosensitive elements |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS6046701B2 (en) |
| BE (1) | BE866247A (en) |
| DE (1) | DE2718130C2 (en) |
| FR (1) | FR2388304A1 (en) |
| GB (1) | GB1575281A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5081000A (en) * | 1989-03-20 | 1992-01-14 | Siemens Aktiengesellschaft | Photosensitive mixture |
| US5258390A (en) * | 1991-10-21 | 1993-11-02 | Imperial Chemical Industries Plc | 9-(3 cyanophenyl) hexahydro-1,8 acridinedione |
| US5340819A (en) * | 1991-10-21 | 1994-08-23 | Imperial Chemical Industries Plc | Method for treating urinary incontinence using 9-(3-nitrophenyl)-3,4,6,7,9,10-hexahydro-1,8-(2H,5H) acridinedione |
| US5455253A (en) * | 1992-10-20 | 1995-10-03 | Zeneca Limited | Heterocyclic derivatives |
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL96545C (en) * | 1954-03-12 | 1900-01-01 | ||
| DE1239940B (en) * | 1962-07-24 | 1967-05-03 | Kalle Ag | Photosensitive recording material for reproduction purposes |
| US3776735A (en) * | 1971-12-28 | 1973-12-04 | Kalle Ag | Light-sensitive copying composition containing a light insensitive polymer and a light sensitive heterocyclic compound |
| DE2242106A1 (en) * | 1972-08-26 | 1974-03-21 | Agfa Gevaert Ag | LIGHT SENSITIVE PHOTOGRAPHIC MATERIAL |
-
1977
- 1977-04-23 DE DE19772718130 patent/DE2718130C2/en not_active Expired
-
1978
- 1978-04-21 FR FR7811887A patent/FR2388304A1/en active Granted
- 1978-04-21 GB GB1596478A patent/GB1575281A/en not_active Expired
- 1978-04-21 BE BE187005A patent/BE866247A/en not_active IP Right Cessation
- 1978-04-21 JP JP53047622A patent/JPS6046701B2/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5081000A (en) * | 1989-03-20 | 1992-01-14 | Siemens Aktiengesellschaft | Photosensitive mixture |
| US5258390A (en) * | 1991-10-21 | 1993-11-02 | Imperial Chemical Industries Plc | 9-(3 cyanophenyl) hexahydro-1,8 acridinedione |
| US5340819A (en) * | 1991-10-21 | 1994-08-23 | Imperial Chemical Industries Plc | Method for treating urinary incontinence using 9-(3-nitrophenyl)-3,4,6,7,9,10-hexahydro-1,8-(2H,5H) acridinedione |
| US5484792A (en) * | 1991-10-21 | 1996-01-16 | Imperial Chemical Industries, Plc | 1,8-(2H,5H)-acridinedione therapeutic agents |
| US5455253A (en) * | 1992-10-20 | 1995-10-03 | Zeneca Limited | Heterocyclic derivatives |
| US5622964A (en) * | 1992-10-20 | 1997-04-22 | Zeneca Limited | Heterocyclic derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2718130B1 (en) | 1978-09-14 |
| JPS53133022A (en) | 1978-11-20 |
| FR2388304B1 (en) | 1983-05-27 |
| BE866247A (en) | 1978-10-23 |
| DE2718130C2 (en) | 1979-05-17 |
| FR2388304A1 (en) | 1978-11-17 |
| JPS6046701B2 (en) | 1985-10-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19970421 |