US3758303A - Photographic imaging of material containing halo azido naphthalenes - Google Patents
Photographic imaging of material containing halo azido naphthalenes Download PDFInfo
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- US3758303A US3758303A US00277453A US3758303DA US3758303A US 3758303 A US3758303 A US 3758303A US 00277453 A US00277453 A US 00277453A US 3758303D A US3758303D A US 3758303DA US 3758303 A US3758303 A US 3758303A
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- azido
- naphthalenes
- light
- photosensitive
- ultraviolet
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- -1 halo azido naphthalenes Chemical class 0.000 title abstract description 15
- 239000000463 material Substances 0.000 title description 9
- 238000003384 imaging method Methods 0.000 title description 5
- 238000000034 method Methods 0.000 abstract description 19
- 239000000203 mixture Substances 0.000 abstract description 17
- 150000002790 naphthalenes Chemical class 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000000576 coating method Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N Methyl ethyl ketone Natural products CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- JVNYVLROXHWCQN-UHFFFAOYSA-N 1,8-diazidonaphthalene Chemical compound C1=CC(N=[N+]=[N-])=C2C(N=[N+]=[N-])=CC=CC2=C1 JVNYVLROXHWCQN-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 229920006385 Geon Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000005041 Mylar™ Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- HUKPVYBUJRAUAG-UHFFFAOYSA-N 7-benzo[a]phenalenone Chemical compound C1=CC(C(=O)C=2C3=CC=CC=2)=C2C3=CC=CC2=C1 HUKPVYBUJRAUAG-UHFFFAOYSA-N 0.000 description 1
- HFFFMTCYIMRHLK-UHFFFAOYSA-N 8-azido-2,4-dibromonaphthalen-1-amine Chemical compound N(=[N+]=[N-])C=1C=CC=C2C(=CC(=C(C12)N)Br)Br HFFFMTCYIMRHLK-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- FLCWLOFMVFESNI-UHFFFAOYSA-N acridine-9(10H)-thione Chemical compound C1=CC=C2C(=S)C3=CC=CC=C3NC2=C1 FLCWLOFMVFESNI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/675—Compositions containing polyhalogenated compounds as photosensitive substances
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/695—Compositions containing azides as the photosensitive substances
Definitions
- Photosensitive compounds, compositions and processes play an essential role in photography and the related arts dealing with the formation of images with the aid of some activating influence, Vsuch as light, heat, etc.
- V such as light, heat, etc.
- Y is a member selected from the group consisting of N3 and -NH2.
- the photosensitive compounds can be readily prepared by chlorination or bromination of the known compound, y8-azido-lnaphthylamine. This can be accomplished by conventional halogen'ation procedures such as those set forth in the text entitled, Reactions of Organic Compounds by W. J. Hickenbottom, Longmans, Green and C0., London, NewYork, 1936, pp. 291-293.
- the corresponding dihalo 1,8-diazidonaphthalenes can be readily formed by converting the amine function to an azide function by conventional procedures such as those disclosed, for example, in U.S. Pat. No. 3,123,621.
- novel, photosensitive compounds of the present invention are 8azido-2,4dibromol-naphthylamine, 8-azid0- 2,4-dichloro 1 naphthylamne, 1,8-diazido-2,4dibr0m0 naphthylamne and 1,8-diazido 2,4 dichloronaphthylamine.
- the photosensitive materials of the present invention comprise a suitable photographic substrate having a photosensitive film or coating deposited thereon.
- the coating is composed of conventional film-forming plastics having one or more of the above photosensitive compounds uniformly incorporated (preferably dissolved) therein.
- Suitable substrates include, for example, such materials as paper, plastic, wood, metal and glass.
- polyvinyl chloride polyethylene, polymethylmethacrylate, polyvinyl acetate, cellulose acetate, copolymers of the corresponding monomers, copolymers of vinylidene chloride and acrylonitrile and mixtures of the above polymers.
- Incorporation of the photosensitive compounds within the film-forming polymer can be conveniently achieved by selecting an organic solvent in which both the polymer and photosensitive compound are soluble.
- Suitable solvents include for example toluene, tetrahydrofuran, benzene, methyl ethyl ketone, mixtures of the above and the like.
- the resulting solution can be applied to the substrate of choice by a variety of standard coating techniques Of the suitable methods of applying the sensitized dope to the structure, the Fixed Blade Method, the Imbibing Method and the Meyer Rod Method are among the preferred techniques.
- the base material is positioned under a fixed blade and an excess of the coating material is placed on the base.
- the base is then passed under the blade to produce a uniform coating having a thickness detetrmined by the distance between the mounted blade and the base material.
- a base stock having a plastic surface is coated with the active compound by passing it under a roller, touching a solution of the azido cornpound.
- the excess coating is removed from the surface by an air knife.
- paper coated with polyvinyl chloride, polyvinyl acetate or polymethylmethacrylate through a solution of l,8-diazido2,4dibromonaphthalene in a solvent such as tetrahydrofuran, methyl ethyl ketone, acetone or toluene or mixtures thereof.
- concentrations of the photosensitive compound and thickness of the coating applied to the substrate may be varied to tailor the photosensitive system so as to achieve the desired degree of image intensity, speed, etc.
- Optimum concentrations and thicknesses will, of course, vary depending upon the particular photosensitive compound, binder material, coating thickness, temperature, time, and other factors.
- satisfactory photoimages can be produced by employing binder compositions having from about to about 20% by weight of the photosensitive compound and coatings having thicknesses in the range of from about 0.05 to about 1.50 mils.
- Preferred concentrations and thicknesses are about by weight and about 0.3 mil, respectively.
- the aromatic azido compounds are themselves generally sensitive to radiation containing wavelengths within the ultraviolet region.
- a sensitizing agent to the polymer binder, the sensitivity can be extended into the range of from 360 my. to 470 m/r or greater.
- the energy transfer of such systems is surprisingly efficient in view of the typically high viscosity of the bindner polymer systems being sensitized.
- sensitized systems permit the use of apparatus equipped with inexpensive and convenient light sources, such as incandescent lamps, and allow projection printing through various optical systems with normal optical glass. They also permit the simultaneous use of both direct and indirect excitation of azido compounds through simultaneous exposure of the photosensitive compounds to both visible and ultraviolet light. Alternatively, enhanced absorption can be achieved by using an ultraviolet absorbing sensitizer in combination with the azido composition.
- Suitable Sensitizers include, for example, fluoranthene, thioxanthone, fluorenone, perylene, benzanthrone, benzophenone, phenazine and thioacridone.
- Sensitizers which absorb light in the visible spectrum are of necessity colored compounds. Where the colors caused thereby are found to be objectionable, one may employ a colorless, ultraviolet absorbing sensitizer or a volatile sensitizer, such as, uorenone, in a gas permeable binder, such as, polyvinyl chloride. The period and degree of heat treatment is adjusted to be suicient to effect volatilization of the uorenone without producing excessive background color-up.
- Optimum relative concentrations of the sensitizer and azido compound will, of course, vary with the particular system being employed. Generally, energy transfer is favored by high concentrations of the photosensitive compound. It is preferred to employ the sensitizer in a sufficient concentration to absorb the incident light. However, excessively high concentrations of the sensitizer will cause complete absorption of the incident light at the surface of the plastic matrix and may thereby reduce the eiciency of the system.
- Imaging is achieved by exposing the photosensitive compositions to patterned activating radiation, namely, an information containing beam of visible or ultraviolet light.
- a convenient source of ultraviolet radiation is provided by lamps which emit a wide range of ultraviolet frequencies.
- a light table equipped with a lm transparency (positive or negative) and a bank of ultraviolet-rich iluorescent lamps, such as, 15 Watt Black Light, No. F15T8-BL by General Electric and Rayonet Photochemical Reactor Lamps, No. RPR 3000A by The Southern New England Ultraviolet Company provides a convenient source of activating radiation.
- Conventional azo printing machines, equipped With high pressure mercury vapor lamps may also be employed. Since they emit both visible and ultraviolet light, they are especially well adapted for use with those compositions having Sensitizers to visible light.
- Absorption of incident light can be maximized by matching the frequencies of the incident light with the absorption frequencies of the photosensitive compound or the sensitizer if one is employed.
- Patterning of the activating radiation can generally be achieved by any of the conventional methods. Suitable methods include passing the light through a lm transparency or a template, use of a cathode ray tube containing an ultraviolet phosphor, such as, a Litton Industries, Inc. Cathode Ray Tube, Ser. No. 4188, which contains a P16 phosphor; and using an ultraviolet pen light, such as Ultraviolet Products, Inc. Pen-Light, or ultraviolet laser, such as might be used in spatial frequency modulation and halographic information storage, etc.
- an ultraviolet pen light such as Ultraviolet Products, Inc. Pen-Light, or ultraviolet laser, such as might be used in spatial frequency modulation and halographic information storage, etc.
- Optimum periods of irradiation will vary widely, depending upon the particular photosensitive composition, opacity of transparency, and light source employed. Exposure for a few Seconds in a conventional azo printer is generally adequate while periods of two minutes or more may be required for a source such as the abovementioned light table.
- Photosensitive compositions were prepared by uniformly coating polyester lm substrates (Mylar) with layers of polyvinyl chloride (Geon 101) which were 0.7 N in the Photosensitive compound.
- the lms were imaged by exposing them through a film transparency to a Abank of black light fluorescent lamps transmitting light in the 300-380 n.m. (peaking at 350 n.m.) region for various equal intervals of time.
- the lms were thereafter heated in an oven at 135 C. for sixty seconds and the optical density of each film was thereafter measured.
- the bromo substituents produce about 50% increases in efficiency.
- Photosensitive compound selected from the group consisting of:
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- General Physics & Mathematics (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Abstract
NOVEL HALO AZIDO NAPHTHALENES AND DRY PHOTOIMAGING PROCESSES AND COMPOSITIONS EMPLOYING SAID NAPHTHALENES ARE DISCLOSED.
Description
3 o. 3 .l 8 5 7 l 3 G N T1. N I A T w 1 C 7 S9 LEl AN IE f RLG mm2 HATY GMHa MM rf m3@ sGOl .w mm BMM l mom C IHi m A R G O T O H P sept. 11, 1973 United States Patent 3,758,303 PHOTOGRAPHIC IMAGING OF MATERIAL CON- TAINING HALO AZIDO NAPHTHALENES Balwant Singh, Stamford, Conn., assignor to American Cyanamid Company, Stamford, Conn. Original application May 26, 1971, Ser. No. 147,117, now Patent No. 3,699,130. Divided and this application Aug. 2, 1972, Ser. No. 277,453
Int. Cl. G03c 5/18 U.S. Cl. .96-27 R 6 Claims ABSTRACT OF THE DISCLOSURE Novel halo azido naphthalenes and dry photoimaging processes and compositions employing said naphthalenes are disclosed.
This application is a divisional of application Ser. No. 147,117, tiled May 26, 1971, now Pat. No. 3,699,130. This invention relates to certain novel halo azido naphthalenes and to dry photoimaging processes and compositions employing said compounds.
Photosensitive compounds, compositions and processes play an essential role in photography and the related arts dealing with the formation of images with the aid of some activating influence, Vsuch as light, heat, etc. For many applications, as in the case of printing on white paper, it is desirable to maximize the neutrality of the image, in addition to achieving good color stability, speed, acuity, resolution and tonal range as well as to achieve the convenience of a dry imaging process employing relatively inexpensive materials.
Accordingly, it is an object of the present invention to provide photosensitive compositions which are suitable for the formation of images having broad spectral characteristics as well as good image stability, acuity, resolution vand tonal range. It is a further object to provide a convenient, dry photoimaging process for the formation of such images. These and other objects of the present invention will become apparent from the description and examples which follow.
In copending application Ser. No. 82,129, tiled Oct. 19, 1970, the use of 1,8-diazidonaphthalene and 8azido1 naphthylamne in photoimaging was disclosed. It has been unexpectedly found that images of enhanced neutrality and optical density can be achieved by employing the novel halo azido naphthalenes selected from the group consisting of:
wherein Y is a member selected from the group consisting of N3 and -NH2.
While applicant does not wish to be limited to a specific theory, it is believed that the halo substituents function as internal heavy atoms to produce internal spin orbital coupling inthe image forming process.
The photosensitive compounds can be readily prepared by chlorination or bromination of the known compound, y8-azido-lnaphthylamine. This can be accomplished by conventional halogen'ation procedures such as those set forth in the text entitled, Reactions of Organic Compounds by W. J. Hickenbottom, Longmans, Green and C0., London, NewYork, 1936, pp. 291-293.
ice
Introduction of the halo substituents may be graphically illustrated as follows:
wherein X is Cl or Br.
The corresponding dihalo 1,8-diazidonaphthalenes can be readily formed by converting the amine function to an azide function by conventional procedures such as those disclosed, for example, in U.S. Pat. No. 3,123,621.
The novel, photosensitive compounds of the present invention are 8azido-2,4dibromol-naphthylamine, 8-azid0- 2,4-dichloro 1 naphthylamne, 1,8-diazido-2,4dibr0m0 naphthylamne and 1,8-diazido 2,4 dichloronaphthylamine.
The photosensitive materials of the present invention comprise a suitable photographic substrate having a photosensitive film or coating deposited thereon. The coating is composed of conventional film-forming plastics having one or more of the above photosensitive compounds uniformly incorporated (preferably dissolved) therein.
Suitable substrates include, for example, such materials as paper, plastic, wood, metal and glass.
Among the suitable conventional polymeric binders, one may mention, for example, polyvinyl chloride, polyethylene, polymethylmethacrylate, polyvinyl acetate, cellulose acetate, copolymers of the corresponding monomers, copolymers of vinylidene chloride and acrylonitrile and mixtures of the above polymers.
Incorporation of the photosensitive compounds Within the film-forming polymer can be conveniently achieved by selecting an organic solvent in which both the polymer and photosensitive compound are soluble. Suitable solvents include for example toluene, tetrahydrofuran, benzene, methyl ethyl ketone, mixtures of the above and the like. The resulting solution can be applied to the substrate of choice by a variety of standard coating techniques Of the suitable methods of applying the sensitized dope to the structure, the Fixed Blade Method, the Imbibing Method and the Meyer Rod Method are among the preferred techniques.
In the Fixed Blade Method, the base material is positioned under a fixed blade and an excess of the coating material is placed on the base. The base is then passed under the blade to produce a uniform coating having a thickness detetrmined by the distance between the mounted blade and the base material.
In the Imbibing Method, a base stock having a plastic surface is coated with the active compound by passing it under a roller, touching a solution of the azido cornpound. The excess coating is removed from the surface by an air knife. By way of illustration, one may mention passing paper coated with polyvinyl chloride, polyvinyl acetate or polymethylmethacrylate through a solution of l,8-diazido2,4dibromonaphthalene in a solvent such as tetrahydrofuran, methyl ethyl ketone, acetone or toluene or mixtures thereof.
The concentrations of the photosensitive compound and thickness of the coating applied to the substrate may be varied to tailor the photosensitive system so as to achieve the desired degree of image intensity, speed, etc. Optimum concentrations and thicknesses will, of course, vary depending upon the particular photosensitive compound, binder material, coating thickness, temperature, time, and other factors. In general, satisfactory photoimages can be produced by employing binder compositions having from about to about 20% by weight of the photosensitive compound and coatings having thicknesses in the range of from about 0.05 to about 1.50 mils. Preferred concentrations and thicknesses are about by weight and about 0.3 mil, respectively.
The aromatic azido compounds are themselves generally sensitive to radiation containing wavelengths within the ultraviolet region. By means of the addition of a sensitizing agent to the polymer binder, the sensitivity can be extended into the range of from 360 my. to 470 m/r or greater. The energy transfer of such systems is surprisingly efficient in view of the typically high viscosity of the bindner polymer systems being sensitized.
Several advantages are provided by the use of sensitized systems. They permit the use of apparatus equipped with inexpensive and convenient light sources, such as incandescent lamps, and allow projection printing through various optical systems with normal optical glass. They also permit the simultaneous use of both direct and indirect excitation of azido compounds through simultaneous exposure of the photosensitive compounds to both visible and ultraviolet light. Alternatively, enhanced absorption can be achieved by using an ultraviolet absorbing sensitizer in combination with the azido composition.
Suitable Sensitizers include, for example, fluoranthene, thioxanthone, fluorenone, perylene, benzanthrone, benzophenone, phenazine and thioacridone.
Sensitizers which absorb light in the visible spectrum are of necessity colored compounds. Where the colors caused thereby are found to be objectionable, one may employ a colorless, ultraviolet absorbing sensitizer or a volatile sensitizer, such as, uorenone, in a gas permeable binder, such as, polyvinyl chloride. The period and degree of heat treatment is adjusted to be suicient to effect volatilization of the uorenone without producing excessive background color-up.
Optimum relative concentrations of the sensitizer and azido compound will, of course, vary with the particular system being employed. Generally, energy transfer is favored by high concentrations of the photosensitive compound. It is preferred to employ the sensitizer in a sufficient concentration to absorb the incident light. However, excessively high concentrations of the sensitizer will cause complete absorption of the incident light at the surface of the plastic matrix and may thereby reduce the eiciency of the system.
Imaging is achieved by exposing the photosensitive compositions to patterned activating radiation, namely, an information containing beam of visible or ultraviolet light.
A convenient source of ultraviolet radiation is provided by lamps which emit a wide range of ultraviolet frequencies. A light table equipped with a lm transparency (positive or negative) and a bank of ultraviolet-rich iluorescent lamps, such as, 15 Watt Black Light, No. F15T8-BL by General Electric and Rayonet Photochemical Reactor Lamps, No. RPR 3000A by The Southern New England Ultraviolet Company provides a convenient source of activating radiation. Conventional azo printing machines, equipped With high pressure mercury vapor lamps may also be employed. Since they emit both visible and ultraviolet light, they are especially well adapted for use with those compositions having Sensitizers to visible light.
Absorption of incident light can be maximized by matching the frequencies of the incident light with the absorption frequencies of the photosensitive compound or the sensitizer if one is employed.
Patterning of the activating radiation can generally be achieved by any of the conventional methods. Suitable methods include passing the light through a lm transparency or a template, use of a cathode ray tube containing an ultraviolet phosphor, such as, a Litton Industries, Inc. Cathode Ray Tube, Ser. No. 4188, which contains a P16 phosphor; and using an ultraviolet pen light, such as Ultraviolet Products, Inc. Pen-Light, or ultraviolet laser, such as might be used in spatial frequency modulation and halographic information storage, etc.
Optimum periods of irradiation will vary widely, depending upon the particular photosensitive composition, opacity of transparency, and light source employed. Exposure for a few Seconds in a conventional azo printer is generally adequate while periods of two minutes or more may be required for a source such as the abovementioned light table.
The enhancement of image neutrality and optical density produced by the presence of the halo substituent is shown in the figure. These characteristics were observed by irradiating polyester film substrates (Mylar by E. I. du Pont de Nemours) uniformly coated with a layer of polyvinyl chloride (Geon 101, d=1.4, by The B. F. Goodrich Chemical Company) having a thickness of from about 0.2 to about 0.3 mil which was 1.0 N in one of the following photosensitive compounds: 8azido2,4-di bromo-l-naphthylamine, 1,8 diazido-2,4dibromonaph thylamine, -8-azido-1-naphthylamine and 1,8-diazidonaphthylamine. Imaging was achieved by exposure through a film transparency to a bank of black light uorescent lamps transmitting light in the 30D-380 n.m. (peaking at 350 n.m.) region for a period of from about 10 to about 30 seconds. The result was a gray-black image of excellent tonal range, resolution and acuity in each case. However, the image neutrality and optical density were in each case substantially enhanced by the presence of the halo substituent.
The processes and compositions of the present invention are further illustrated by the following examples which are not to be taken as limitative thereof. All parts and percentages herein are by weight unless otherwise indicated.
EXAMPLE 1 1-amino-8-azido-2,4-dibromonaphthylamine A solution of 1-amino-8-azidonaphthylamine (2.3 g., 0.0125 mole) in ml. of glacial acetic acid was treated with a solution of bromine (4.0 g., 0.025 mole) in 50 ml. of glacial acetic acid The precipitated hydrobromide was removed by iltration and washed with ether. The nearly white precipitate was digested with aqueous NaHCO3. The dibromoaminoazide was extracted with ether, washed, dried and filtered through charcoal. Removal of ether left a residue Which was recrystallized from ether to yield 3.1 g., 82% of the desired product having an M.P. of 127 130 C. Identification was made by infrared and elemental analysis:
Calcd. for C10H6N4Br2 (percent): C, 35.10; H, 1.75; N, 16.40; Br, 46.95. Found (percent): C, 35.38; H, 1.46; N, 16.33; Br, 47.19.
EXAMPLE 2 1,8-diazido-2,4dibromonaphthylamine A solution of l-amino-8-azido-2,4-dibromonaphthylamine (500 mg., 1.46 moles) in 50 ml. of acetic acid was mixed with 10 ml. of concentrated hydrochloric acid and cooled to 5 C. in an ice bath. A solution of NaNOZ (280 mg., 0.4 mole) in water (1 ml.) was added dropwise with stirring. After 1/2 hour, the mixture was poured into an excess of NaN3 (2 g., in 100 ml. of ice-water mixture). The precipitate of the diazide was removed by filtration, dissolved in ethyl ether, dried over anhydrous MgSO4 and filtered through charcoal. Removal of the ether left the desired product as a residue. It was recrystallized from n-hexane to yield 334 mg. (65%), M.P. 130 C.132 C. Identification was made by infrared and elemental analysis:
Calcd. for CH6N4Br., (percent): C, 32.60; H, 0.90; N, 22.80; Br, 43.50. Found (percent): C, 32.85; H, 0.84;
N, 23.00, Br, 43.75.
EXAMPLE 3 The enhancement of optical density produced by the halo substituents is demonstrated by the following tests.
Photosensitive compositions were prepared by uniformly coating polyester lm substrates (Mylar) with layers of polyvinyl chloride (Geon 101) which were 0.7 N in the Photosensitive compound. The lms were imaged by exposing them through a film transparency to a Abank of black light fluorescent lamps transmitting light in the 300-380 n.m. (peaking at 350 n.m.) region for various equal intervals of time. The lms were thereafter heated in an oven at 135 C. for sixty seconds and the optical density of each film was thereafter measured. In each case, as shown by the data presented in Table I below, the bromo substituents produce about 50% increases in efficiency.
TABLE I 1,8-dlazido- 1,8-diazidonaphtha- 2,4-dibromo- Exposure lene naphthatime (min.) (OD) lene Thickness of coating=0.2 mil.
plastic having incorporated therein a Photosensitive compound selected from the group consisting of:
Y NaY References Cited UNITED STATES PATENTS 1,845,989 2/ 1932 Schmidt et al. 96-91 N 2,692,826 10/ 1954 Neugebauer et al. 96--91 N X 3,072,485 1/1963 Reynolds, et al. 96-91 N X 3,092,494 6/ 1963 Sus et al. 96-75 X 3,282,693 11/1966 Sagura et al. 96-49 3,519,424 7/1970 Reynolds et al. 96-91 N 3,660,093 5/ 1972 Ranz 96-49 X OTHER REFERENCES Kosar, I., Light-Sensitive Systems, Wiley & Sons, 1965, pp. 276-282, 330-336, 361-363, S-372, 376.
Hoffmann et al., I. Chem. Soc. C0., 1969, pp. 769-772. Reiser et al., Trans Faraday, Soc., 1968, pp. 1806-1815.
CHARLES L. BOWERS, JR., Primary Examiner U.S. Cl. X.R. 96-49
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US14711771A | 1971-05-26 | 1971-05-26 | |
US27745372A | 1972-08-02 | 1972-08-02 |
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US00277453A Expired - Lifetime US3758303A (en) | 1971-05-26 | 1972-08-02 | Photographic imaging of material containing halo azido naphthalenes |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US4622284A (en) * | 1984-03-01 | 1986-11-11 | Digital Recording Corporation | Process of using metal azide recording media with laser |
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1972
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US4622284A (en) * | 1984-03-01 | 1986-11-11 | Digital Recording Corporation | Process of using metal azide recording media with laser |
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