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Publication numberUS3758303 A
Publication typeGrant
Publication dateSep 11, 1973
Filing dateAug 2, 1972
Priority dateMay 26, 1971
Publication numberUS 3758303 A, US 3758303A, US-A-3758303, US3758303 A, US3758303A
InventorsSingh B
Original AssigneeAmerican Cyanamid Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Photographic imaging of material containing halo azido naphthalenes
US 3758303 A
Abstract  available in
Previous page
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Claims  available in
Description  (OCR text may contain errors)

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.


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

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4622284 *Mar 1, 1984Nov 11, 1986Digital Recording CorporationProcess of using metal azide recording media with laser
U.S. Classification430/147, 430/616, 430/346, 430/196, 430/194
International ClassificationG03C1/695, G03C1/675
Cooperative ClassificationG03C1/695, G03C1/675
European ClassificationG03C1/695, G03C1/675