US3923521A - Ultraviolet holdback of nonsilver photosensitive systems by incorporating therein certain organic additives - Google Patents

Abstract

Ultraviolet holdback of non-silver photosensitive compositions such as those described in U.S. Pat. Nos. 3,042,517 to 3,042,519 and similar non-silver free-radical compositions, is improved by the addition thereto of certain aromatic compounds, namely: aromatic heterocyclic compounds containing nitrogen as part of the ring systems, quinone compounds, pyrazolones, aromatic diamines, and aromatic esters of acetic acid.

Description

United States Patent [191 Hazy et al.

[ 5] Dec. 2, 1975 1 ULTRAVIOLET HOLDBACK OF NONSILVER PHOTOSENSITIVE SYSTEMS BY INCORPORATING TI'IEREIN CERTAIN ORGANIC ADDITIVES [75] Inventors: Andrew C. Hazy, Mentor; John E.

Shirey, Bedford; Lothar Ramins, Middlefield, all of Ohio [73] Assignee: Horizons Incorporated a division of Horizons Research Incorporated, Cleveland, Ohio 221 Filed Jan. 31, 1973 211 Appl. No.: 328,495

[52] US. Cl 96/90 R; 96/115 P [51] Int. Cl. G03C 1/52 [58] Field of Search 96/90 R, 115 P, 88

[56] References Cited UNITED STATES PATENTS 3,351,467 11/1967 Sprague et al. 96/90 3,502,476 3/1970 Itano et al 96/90 3,527,639 9/1970 Moraw 6/90 3,600,179 8/1971 Yamada ct al 96/90 3,620,748 11/1971 Fichter 96/90 3,790,376 2/1974 Hashine et al. 96/90 Primary Examinen-Won H. Louie, Jr. Attorney, Agent, or Firm-Lawrence 1. Field [57] ABSTRACT 8 .Claims, No Drawings ULTRAVIOLET HOLDBACK or NONSILVER PHOTOSENSITIVE SYSTEMS BY INCORPORATING THEREIN CERTAIN ORGANIC ADDITIVES i This invention relates to photosensitive compositions and to photosensitive films based on such compositions. More particularly, it relates to improved ultraviolet holdback characteristics obtained from such photo- The importance of this invention will be apparent from the fact that in a significant portion of the photographic processing requiring the need forduplication of information that may be available from a negative taken in a camera, in which relatively large numbers of such duplicates are required, ultraviolet light sources are commonly used in the printers involved in such duplication in view of the high density of illumination that can be packed in the small space in contradistinction to substantially lower levels of illumination that may be provided by visible light sources. Since ultraviolet is the commonly used source of illumination for duplication purposes and since duplicates may be made from duplicates, the sensitometric properties of the photographic system in the ultraviolet are important and particularly with regard to the amount of optical ultraviolet density that can be achieved in the material on suitable exposure to ultraviolet light. Intermediate masters exhibiting such high optical density in the image area, even though the density in the visible may be very low, are 40 then suitable for use as stencils to enable one to copy the information onto a material which again will require the use of ultraviolet light for exposure purposes but in which the visible density isvery high. In reality, this is a process of multigeneration and the improved ultraviolet 'holdback described in this specification is of fundamental importance in order to achieve the design purpose.

Compounds useful in the practice of this invention fit into the following general classificationsz aromatic or partially aromatic heterocyclic materials containing nitrogen as part of the ring system, quinone compounds, aromatic diamines, and aromatic esters of acetic acid.

The photosensitive compositions to which the present invention is particularly applicable are non-silver photosensitive compositions comprising an N-vinyl color forming compound and an activator, usually an organic halogen compound or a sulfur containing compound as described in the following U.S. patents, among others:

N-Vinyl Color Forming Compounds U.S. Pat. Nos. 3,042,517; 3,042,518 3,042,519; 3,056,673

Organic Halogen Activator Compounds U.S. Pat. Nos. 3,042,515; 3,147,117

Sulfur Containing Activator Compounds U.S. Pat. No. 3,285,744 V Sulfur and Halogen Containing Activator Compounds U.S. Pat. No. 3,113,024

The disclosure of said patents are intended to be incorporated herein by reference.

The compounds enumerated below are representative ofspecificcompoundswithin the above classes and are intended to be illustrative and are not to be considered a complete listing of all'of those which are suitable for the present invention:

1. N-Vinyl Color Forming Compounds The N-vinyl color forming compounds which are utilized in the photosensitive compositions of this invention are those described in U.S. Pat. Nos. 3,052,517; 3,042,518; 3,042,519; and 3,056,673, among others. Suitable compounds include: N-vinyl-carbazole, N- vinylphenyl-a-naphthylamine, N-vinylpyrrolidone, N- vinylsuccinimide, N-vinylacetanilide, N-vinylphenylacetamide, Nvinylmethylacetamide, and N- vinyldiglycolylimide.

. 2. Activators a. Organic Halogen Compounds The organic halogen compounds which are useful in the light sensitive compositions of this invention are those represented by the general formula AC-X;, wherein A represents a monovalent radical which may be halogen (Cl, Br or I), H, alkyl, substituted alkyl including halogen substituted alkyl, aryl, substituted aryl, aroyl, and arylalkyl and wherein each X represents a halogen atom which may be either chlorine, bromine or iodine, it being understood that not all of the X atoms need be alike. Preferred compounds are halogen substituted alkanes, e.g. CBr CHI C HBr CI etc., and a,a,a-tribromoacetophenoner b. Sulfur Containing Compounds The sulfur containing compounds which are utilized in the photosensitive compositions of the present invention are those represented by either the formula R-SH or the formula R-S-SR wherein each R represents an aryl or heterocyclic ring. Suitable compounds include Z-mercaptobenzothiazole, S-methoxy- Z-mercaptobenzothiazole, l-phenyl-S -me rcaptotetrazole and pentachlorobenzenethio-bis(dimethylthiocarbonyDdisulfide. c. Sulfur and Halogen Containing'Compounds Activator compounds containing both halogen and sulfur and which are suitable for the compositions of the present invention include the sulfonyl and sulfenyl halides described in U.S. Pat. No. 3,1 13,024, e.g., 2,4- dinitrobenzenesulfonyl chloride, p-chlorobenzenesulfonyl chloride, o-nitrobenzenesulfenyl chloride and pentachlorobenzenesulfenyl chloride.

3. Binder As described in the above noted patents, the photosensitive compositions are preferably formulated with av film forming binder and are cast as a thin film from solution usually as a thin coating on a suitable substrate. Among the binders which can be used are solutions of polystyrene, copolymers of styrene and acrylonitrile, polyphenylene oxide, polycarbonate, polyvinylbutyral, suitable combinations of the above, and others such as those described in U.S. Pat. Nos. 3,100,703 and 3,147,117. The compositions have been utilized without a binder, for example, when imbibed in a paper or other porous substrate. a

4. Additional Constituents Manycompounds which have been added for specific benefits to the aforementioned photosensitive compositions are fully described in the above noted patents, including compounds to sensitize the composi- 5. Organic Compounds Producing Imagery I-laving Improved Ultraviolet l-loldback The organic compounds the addition of which to the otherwise known photosensitive compositions produces imagery having improved ultraviolet holdback, the use of which comprises the present invention, are compounds found in the following general classes: aromatic or partially aromatic heterocyclic materials containing nitrogen as part of the ring system, quinone compounds, aromatic diamines, and aromatic esters of acetic acid. Examples of heterocyclic materials which have been found suitable include: indole, quinoline, acridine, acridan, phenoxazine, quinazoline, phenazine and 2-phenylindole. Quinone compounds which are useful for the present invention include: l-amino-4- hydroxy-9, 1 O-anthraquinone, 1-amino-4-benzamido- 9,10-anthraquinone, 1 ,4-diamino-9,10-anthraquinone, l-amino-S -benzamido-9, l O-anthraquinone, l ,S-dibenz amido-9, l O-anthraquinone, 1 ,4-diamino-2,3-dichloro- 9,10-anthraquinone and 2-amino-1,4-naphthoquinone. Suitable aromatic diamines include: o-phenylenediamine, p-phenylenediamine, N-phenyl-p-phenylenediamine, N-phenyl-o-phenylenediamine, and the like. Aromatic esters of acetic acid which are useful for the present invention include: phenyl acetate, o-methoxyphenyl acetate, 4-chlorophenyl acetate, 2,4- dichlorophenyl acetate and 2,4-dimethoxyphenyl acetate- Proportions Suitable proportions of the subject U.V. holdback producing compounds range from 0.02 part to up to 2 parts by weight of such compound, for each part by weight of the N-vinyl color forming compound in the composition and depends to some extent on the solubility of the particular additive in the binder-solvent used.

Base

The formulations employed in this invention can be applied to any suitable substrate such as cellulose acetate, polyesters such as polyethylene terephthalate as defined by the trade names Mylar (E.l. duPont) and Celanar (Celanese Corporation), paper, cloth, glass, etc.

. Fixing Fixing photosensitive compositions employed in this invention after exposure, is accomplished by heat or by solvent wash as described in the prior art.

EXAMPLES The following examples are illustrative of the ways in which the compounds referred to in this invention were used and are not intended as limitative thereof.

' 2,6-di-t-butyl-p-cresol, 220 mg of triethylamine, and 10 EXAMPLE 1 A binder solution was prepared by dissolving 10 g of polyvinylbutyral in ml of methylene chloride, 25 ml of chlorobenzene and 5 ml of triethylamine To 6 ml of this solution was added 285 mg of N-vinylcarbazole, 700 mg of carbon tetrabromide, 50 mg of 2,6-di-tbutyl-p-cresol and 10 mg of triphenyl stibene. The resulting solution was coated 0.003 inch thick (wet) on a sheet of polyethylene terephthalate and then dried at C for 30 seconds. This film was exposed to a high pressure mercury arc lamp and then fixed by heating to 160C for 2 minutes. No visible image was obtained, but image density over base plus fog, as read through a 366 nm filter, was 0.63 density units. An otherwise identical film was prepared, except that 10 mg of lamino-5-benzamido-9,lO-ahthraquinone was added to the formulation. After identical exposure and processing, this film produced a visible density of only 0.04, while the net density at 366 nm was 0.97.

EXAMPLES 2 and 3 A film was prepared as described in Example 1 except that mg of 4-amino-2,3-dimethyl-1-pheny1-3- pyrazolin-S-one was added instead of the 1-amino-5- benzamido-9,IO-anthraquinone. This film produced a net density of 0.20 (visible) and a net density of 2.24 when read through a 366 nm filter. Another film was prepared using 100 mg of 2-phenylindole as the additive and this film gave a net density of 1.40 at 366 nm and only 0.07 in the visible.

EXAMPLE 4 A film was prepared from the following formulation: 285 mg of N-vinylcarbazole, 700 mg of carbon tetrabromide, 50 mg of 2,6-di-t-butyl-p-cresol, 220 mg of triethylamine, and 10 mg of triphenyl stibene in'6 ml of a 10% solution of polyvinylpyrrolidone in 3:1 methylene chloride-chlorobenzene. That solution was coated 0.003 inch thick (wet) on polyethylene terephthalate and the film was dried at 90C for 30 seconds. Exposure to a high pressure mercury arc lamp was followed by fixing at C for 2 minutes. The net density (366 nm) produced was 1.35. An otherwise identical film wasprepared with 100-mg of indole as an additive and this film produced a net density of 1.72 after identical exposure and processing.

EXAMPLE 5-7 Films were prepared as described in Example 4 except that the additive for each film was different. A film containing 100 mg of 2-phenylindole gave a net density of 1.57, a film with 100 mg of acridine in it produced a net density of 1.50 and a film which contained 100 mg of 4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one as the additive gave a net density of 2.50. Exposure and processing were identical with that of Example 4.

EXAMPLES 9-11 A control film was prepared from 285 mg of N-vinylcarbazole, 700 mg of carbon tetrabromide, 50 mg of mg of triphenylstibene in 6 ml of a 10% solution of polyarylsulfone in 3:1 methylene chloride-chlorobenzene. This film gave a net density (366 nm) of 1.38 and a visible net density of 0.05 after exposure and fixing as described in Example 1. To this control formulation was added 10 mg of 1-amino-5-benzamido-9,10-

anthraquinone' and the resulting film produe d a net density of 1.58 (366 nm) "and 0.18 in the visible. A similar film was made from the control formulation with 100 mg of Z-ph'enylin'drfleas the additive and this film gave a net'density of 0.15."Whe'n the control formulation was treated with 100 mg of 4-arnino-2,3-dimethyl- 1-phenyl-3-pyrazolin-5=o'ne; the resulting *film' gave 2.56 net density at 366 rim; with only 0.30 net visible density. I i 1 EXAMPLES 12-16 The control formulation'used for'examples 9- 11 was coated'from a solution ofp'oly'carbonate in 3:1 methylene chloride-chlorobenzene instead of polyarylsulfone. This solution produced a film which gave a net density (366 nm) of 1.74. Similar polycarbonate films were then prepared using the following additives: 1O

. EXAMPLES 21-43 mulation was used as a control anda series of organic compounds-wereevaluate'd as additives, in 100 mg concentrations, to the contr'olsThe list of materials and the results obtained from the respectivefilms' are shown in Table 1. It should be noted that many of the additives produced improved ultraviolet holdback without significantly increasing the visible density'so that these compositions are particularly useful for the production of see-through masks.

TABLE I Effect of Additives on Ultraviolet (366 nm) Holdback Example net Density net Density Numbers Additive (366 nm) (visible) j None (control) 1.30 0.04 21 lndole 1.54 0.16

22 Quinoline 1.95 0.05 23 Acridine 1.49 '0. l 8 24 Acridan a 2.20 0.24 25 1-Amino-4-hydroxy-9, 1 O-anthraquinone l .45 0.30 26 1,4-Diamino-9, l O-anthraquinone 1.69 none 27 1-Amino-4-benzamido-9, IO-anthraquinone 1.60 none 28 l-Amino-S-benzamido-Q, IO-anthraquinone 1 .80 0.14 29 1,5 -Dibenzamido-9, 1 O-anthraquinone 1.38 0.03 30 l ,4-Diamino-2,3-dichloro-9,10-anthraquinone l .42 none 31 2-Amino-l ,4-naphthoquinone 1 .46 0.07 32 Phenoxazine 1.52 0.08 3 3 Quinazoline 1.60 0.04 34 Quinoxaline l .53 0.06 35 Phenazine 1.67 0.04 36 4-Amino-2,3-dimethyll -phenyl-3-pyrazolin-5 -one 1 .92 0.22 37 2,3-Dimethyl-4-dimethylamino-1-phenyl-3- pyrazolin-S-one 1.70 0.08 38 1 3-Diphenyl-5-pyrazolone 1 .54 0.10 39 Phenyl acetate 1.38 0.04 40 o-Methoxyphenyl acetate 1.59 0.04 41 o-Phenylenediamine 1.50 0.02 42 N-Phenyl-p-phenylenediamine l .40 0.08 43 Z-Phenylindole 1.76 0.22

EXAMPLE 44 mg of acridan gave net density 2.32 while 100 mg of acridan gave 2.53 net density; 10 mg of l-amino-S-benzamido-9,IO-anthraquinone gave net density of 1.83; 100 mg of 4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin- 5-one produced 2.62 net density; 100 mg of 2- phenylindole gave a net density of 2.00.

EXAMPLES 17-20 A formulation composed of 285 mg of N-vinylcarbazole, 10 mg of triphenyl stibene, 50 mg of 2,6-di-tbutyl-p-cresol, 700 mg of carbon tetrabromide, 220 mg of triethylamine and 6 ml of a 10% solution of polystyrene in 3:2 toluene-methyl ethyl ketone was coated 0.003 inch thick (wet) on polyethylene terephthalate and dried at 90C for 30 seconds. The resulting film was exposed and fixed as described in Example 1 and gave 1.76 net density at 366 nm. When this formulation was coated with 100 mg of acridan as an additive, the resulting film produced net density of 2.40 after identical exposure and fixing.

Similarly, a film utilizing 100 mg of o-methoxyphenyl acetate as an additive gave 2.01 net density; using 10 mg of quinoline gave a film which produced 2.11 net density.

A film was coated on polyethylene terephthalate from a solution consisting of 285 mg of N-vinylcarbazole, mg of Z-mercaptolbenzothiazole, 35 mg of carbon tetrabromide, 64 mg of triethylamine, 1 cc of acetone and 6 cc of 18% polystyrene in 2:1 toluene ethylene dichloride. The film was exposed as in example l and then heated to C for 1 minute to produce 0.11 net density (visible) and 1.85 net density at 366 nm. An otherwise identical film was prepared, except that 50 mg of phenoxazine was added. After identical exposure and processing, the film gave 0.11 density (visible) and 2.28 net density at 366 nm.

EXAMPLE 45 7 We claim: 1. In a non-silver photosensitive composition comamino-4-hydroxy-9,lO-anthraquinone, 1-amino-4- benzamido-9, l -anthraquinone, 1,4-diamino-9, l 0-- prising: I anthraquinone, l amino--benzamido-9,l0- l. at least one N-vinyl amine compound which forms r anthraquinone, l-5-dibenzamido-9, IO-anthraquia color when exposed to. a dose of suitable radia- 5 none, l,4-diamino-2,3-dichloro-9,IO-anthraqui- -tion inthe presence of an activator; none and Z-amino-l,4-naphthoquinone, phenylene 2. at leastone such activator for said color forming diamines and phenylacetates. -1 a N-vinyl amine compound, said activator being se- 2. The composition of claim 1 in which the proporlected from the group consisting of (a) organic l0 tiori of N-vinyl compound and the compound produchalogen compounds represented by the general formula QCX wherein Q represents a monovalent radical selected from the group consisting of Cl, Br,"l, H, alkyl, aryl, aroyl and arylalkyl, and each X is a halogen atom selected from the group consisting of Cl, Br and l; (b) sulfur containing organic compounds represented by the formula RSH or RSSR in which each R represents an aryl or heterocyclic ring; and (c) sulfonyl and sulfenyl halides; the improvement of which consists in the incorporation in said composition of 3. at least one organic compound which produces imagery having improved ultraviolet holdback said 8. A photographic element comprising a support and compound being selected from the group consista coating thereon comprising the composition of claim ing of indole, quinoline, acridine, acridan, phenoxl. azine, quinazoline, phenazine, 2-phenylindole, lv ing imagery with improved ultraviolet holdback is between about 5021 and 1:2.

3. The composition of claim 1 in which the N-vinyl compound is N-vinylcarbazole and the holdback compound is l -amino-5-benzamido-9, l O-anthraquinone.

4. The composition of claim 1 wherein the holdback compound is an indole.

5. The composition of claim 1 wherein the holdbac compound is an anthraquinone.

6. The composition of claim 1 wherein the holdback compound is an phenyl diamine.

7. The composition of claim 1 wherein the holdback compound is an phenyl ester of acetic acid.

Claims (13)

1. IN A NON-SILVER PHOTOSENSITIVE COMPOSITION COMPRISING:

1. AT LEAST ONE N-VINYL AMINE COMPOUND WHICH FORMS A COLOR WHEN EXPOSED TO A DOSE OF SUITABLE RADIATION IN THE PRESENCE OF AN ACTIVATOR;

2. AT LEAST ONE SUCH ACTIVATOR FOR SAID COLOR FORMING N-VINYL AMINE COMPOUND, SAID ACTIVATOR BEING SELECTED FROM THE GROUP CONSISTING OF (A) ORGANIC HALOGEN COMPOUNDS REPRESENTED BY THE GENERAL FORMULA 1-C-X3 WHEREIN Q REPRESENTS A MONOVALENT RADICAL SELECTED FROM THE GROUP CONSISTING OF CL, BR, I, H, ALKYL, ARYL, AROYL AND ARYLALKYL, AND EACH X IS A HALOGEN ATOM SELECTED FROM THE GROUP CONSISTING OF CL, BR AND I; (B) SULFUR CONTAINING ORGANIC COMPOUNDS REPRESENTED BY THE FORMULA RSH OR RSSR IN WHICH EACH R REPRESENTS AN ARYL OR HETEROCYCLIC RING; AND (C) SULFONYL AND SULFENYL HALIDES; THE IMPROVEMENT OF WHICH CONSISTS IN THE INCORPORATION IN SAID COMPOSITION OF

2. The composition of claim 1 in which the proportion of N-vinyl compound and the compound producing imagery with improved ultraviolet holdback is between about 50:1 and 1:2.

2. at least one such activator for said color forming N-vinyl amine compound, said activator being selected from the group consisting of (a) organic halogen compounds represented by the general formula Q-C-X3 wherein Q represents a monovalent radical selected from the group consisting of Cl, Br, I, H, alkyl, aryl, aroyl and arylalkyl, and each X is a halogen atom selected from the group consisting of Cl, Br and I; (b) sulfur containing organic compounds represented by the formula RSH or RSSR in which each R represents an aryl or heterocyclic ring; and (c) sulfonyl and sulfenyl halides; the improvement of which consists in the incorporation in said composition of

3. at least one organic compound which produces imagery having improved ultraviolet holdback said compound being selected from the group consisting of indole, quinoline, acridine, acridan, phenoxazine, quinazoline, phenazine, 2-phenylindole, 1-amino-4-hydroxy-9,10-anthraquinone, 1-amino-4-benzamido-9,10-anthraquinone, 1,4-diamino-9,10-anthraquinone, 1-amino-5-benzamido-9,10-anthraquinone, 1-5-dibenzamido-9,10-anthraquinone, 1,4-diamino-2,3-dichloro-9,10-anthraquinone and 2-amino-1,4-naphthoquinone, phenylene diamines and phenylacetates.

3. The composition of claim 1 in which the N-vinyl compound is N-vinylcarbazole and the holdback compound is 1-amino-5-benzamido-9,10-anthraquinone.

3. AT LEAST ONE ORGANIC COMPOUND WHICH PRODUCES IMAGERY HAVING IMPROVED ULTRAVIOLET HOLDBACK SAID COMPOUND BEING SELECTED FROM THE GROUP CONSISTING OF INDOLE, QUINOLINE, ACRIDINE, ACRIDAN, PHENOXAZOLINE, PHENAZINE, 2-PHENYLINDOLE, 1-AMINO-4-HYDROXY-9,10ANTHRAQUINONE, 1-AMINO-4-BENZAMIDO-9,10-ANTHRAQUINONE, 1,4-DIAMINO-9,10-ANTHRAQUINONE, 1-AMINO-5-BENZAMIDO-9,10-ANTHRAQUINONE, 1-5-DIBENZAMIDO-9,10ANTHRAQUINONE, 1,4-DIAMINO-2,3-DICHLORO-9,10ANTHRAQUIONE AND 2-AMINO-1,4-NAPHTHOQUINONE, PHENYLENE DIAMINES AND PHENYLACETATES.

4. The composition of claim 1 wherein the holdback compound is an indole.

5. The composition of claim 1 wherein the holdback compound is an anthraquinone.

6. The composition of claim 1 wherein the holdback compound is an phenyl diamine.

7. The composition of claim 1 wherein the holdback compound is an phenyl ester of acetic acid.

8. A photographic element comprising a support and a coating thereon comprising the composition of claim 1.