US3907569A - Ultraviolet holdback of nonsilver photosensitive systems by incorporating therein certain organic additives - Google Patents

Abstract

A non-silver, photosensitive composition comprising: at least one aminoaryl ethylene color forming compound and at least one activator for said color forming compound, wherein the composition includes in addition at least one organic compound the addition of which produces imagery having improved ultraviolet holdback, such compounds being selected from the group consisting of heterocyclic compounds, quinone compounds, multifunctional aromatic hydroxy compounds and aromatic carbonyl containing compounds.

Description

United States Patent n91 Hazy et al.

[ 1 Sept. 23, 1975 ULTRAVIOLET HOLDBACK OF NONSILVER PHOTOSENSITIVE SYSTEMS BY INCORPORATING THEREIN 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 [212] Filed: Jan. 31, 1973 [21] Appl. No.: 328,428

[52] US. Cl 96/90 R; 96/115 P [51] Int. C1. G03C 1/52 [58] Field of Search 96/90 R, 90 PC, 88, 115 P [56] References Cited UNITED STATES PATENTS 3,351,467 11/1967 Sprague et al. 96/90 R 3,502,476 3/1970 Itano et a1. 96/90 R 3,510,304

5/1970 Fichter et a1 96/90 R 3,527,639 9/1970 Moraw 96/90 R 3,533,792 10/1970 Petro ct a1. 96/90 R 3,560,216 2/1971 Hori ct a1 96/90 R 3,579,342 5/1971 Strilko 96/90 R 3,620,748 11/1971 Fichter 96/90 R 3,642,479 2/1972 Allan et a1. 96/90 R 3,708,297 1/1973 Poot 96/90 R 3,712,817 1/1973 Hazy 96/90 R Primary ExaminerWon H. Louie, Jr. Attorney, Agent, or FirmLawrence 1. Field [57] ABSTRACT 9 Claims, N0 Drawings ULTRAVIOLET HOLDBACK OF NONSILVER PHOTOSENSITIVE SYSTEMS BY INCORPORATING THEREIN CERTAIN ORGANIC ADDITIVES 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 photosensitive compositions by the incorporation therein of certain organic compounds as described below'. The improved ultraviolet holdback of said compositions makes them especially suitable for use in the preparation of intermediate masters for duplication purposes and for photomasks. Some of these compounds improve photosensitive compositions even fu-rther, giving the additional advantage of being particularly useful for the production of see-through masks, since they increase the ultraviolet holdback with little or no increase in visible density so that't'he resulting mask retains transparency to visible radiation. 5

The importance of this invention will'be apparent from the fact that in a significant portion of t he photographic processing requiring the need for duplication of information that may be available from a negative taken in a camera, inwhich 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 materialon 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 then suitable for use as stencils to enable one to copy information onto a material which again will require the use of ultraviolet light for exposure purposes, but in which the visible density is very high. In reality, this is a process of multigeneration and the improved ultraviolet holdback described in thisspecification is of fundamental importance'in order toachieve the design purpose.

Compounds useful in the practice ofthis invention fall into the following general classes: heterocyclic Ethylene Compounds 3,042,5l5; 3,l47,l l7

Organic Halogen Compounds Sulfur Containing Compounds 3,285,744 Sulfur and Halogen Containing Compounds t ,The' disclosures of said patents are intended to be incorporated herein by reference. The compounds enumerated below are representative of specific compounds within 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. Color Forming Compounds Suitable color forming compounds useful in the pracv tice of this invention are ethylene compounds as dc scribed in U.S. Pat. Nos. 3,510,304 and 3,533,792 which may be represented by the formula ll R/XR,

wherein R and R are each a monovalent radical represented by the formula 2. Activators a. Organic Halogen Compounds l.

The organic halogen compounds which are suitable in the light sensitive compositions to which the present invention is applicable include those represented by the general formula A-C--X wherein A represents 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 11,04, a-tril bromoacetophenone. I b. Sulfur Containing Compounds The sulfur containing compounds which are suitable in the photosensitive compositions to which the present invention is applicable are those represented by either the formula R-SH or the formula RSS-R wherein each R represents an aryl or heterocyclic ring,

Suitable compounds include 2-mercaptobenzothiazole 5-methoxy-Z-mercaptobenzothiazole, mercaptotetraz'ole "and pentachlorobenzenethio-l bis(dimethyl-thiocarbonyl) disulfide. c. Sulfur and Halogen Containing Compounds Activator compounds containing both halogen and sulfur and which are suitable for the present invention include the sulfonyl and sulfenyl halides described in US; Pat. No. 3,1 13,024, e.g., 2,4-dinitrobenzenesulfo nyl chloride, p-chlorobenzenesulfonyl chloride, 0- nitrobenze'nesulfenyl chloride and pentachloroben- -zeri esulfenyl chloride.

3. Binder As described in the above noted patents, the photo- 3,510,304 and 3,533,792, for example.

sensitive compositions are preferably formulated with a film forming binder and are cast as a thin film from solution usually as a thin coating on a suitable sub strate. Among the binders which can be used are solutions of polystyrene, copolymers of styrene and 'acrylonitrile, polyph'enyleneoxide, polycarbonate, polyvinylbutyral, suitable combinations of the above, and others such as those described in US. 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.

4, Additional Constituents Many additional compounds which have been added to the aforementioned photosensitive compositions for specific benefits are fully described in the above noted patents, including compounds to sensitize the compositions to certain wavelengths of light, stabilizers to permit storage of the compositions, additives to modify the color of the image produced by exposure to light, and additives, which. facilitate fixing of the compositions after exposure. The present invention is applicable to compositions including one or more of such additives.

5. Organic Compounds Producing Imagery Having Improved Ultraviolet Holdback dihydroanthracene. Suitable carbonyl compounds include acetanilide, 'phenyl acetate and N-acetyl-N- phenylhydrazine. Other compounds suitable for the, practice. of this invention include those which have structures fitting more than one of the outlinedgclasses as, for example: l-amino-4-hydroxy9,10- anthraquinone, -amino-4.-benzamido-9, l0- anthraquinone, l,4-dihydroxy-9,'lO-anthraquinone, 2-,

Celanar (Celanese Corporation). paper, cloth, glass, ctc. Fixing Fixing of the exposed photosensitive compositions employed in this invention is accomplished by heat or by solvent above.

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.

EXAMPLE I A solution of 130 mg of l,1-bis(4-dimethylaminophenyl)- ethylene,'50 mg of 2,6-di-t-butyl-p-cresol, 10 I mg of triphenyl'stibene,280 mg of iodoform, 100 mg of triethylamine, 75 mg of methyl oleate and 3 mg of 1,2-riaphthoquinone in 6 cc of a ,10 percent solution of polyphenylene oxide in 1:1 chloroform-chlorobenzene was coated 0.003 inch (wet thickness) on a polyester' substrate and dried for 2 minutes at 90C. The resulting film was exposed to a high pressure mercury arc lamp through an Eastman No. 2 step'wedge and given a maximum exposure of 90"mj/ct'n The film was fixed by heating to 160C for'2 minutes and gave 'a net maxi mum optical density (over base plus fog) of 1.40 when read with a UV. densitometer using a filter which 7 transmitted only 366.0 nm radiation. An otherwise identical film was prepared, but without the 'naphthoquinoneyMaximum optical density over base plus fog hydroxy-3*naphthoic'acid anilide, 2-hydroxycarbazole- 3-carboxylic acid- P.-chloroanilide and 2--hydroxyabenzocarbazole-3-carboxylic acid p-methoxyanilide.

Proportions 9 Suitable .proportions of the :U.V.: holdback compounds'range from 0.02 part to up to 2 parts by weight of compound, for each part by weight of the color forming compound in the composition and depends to some extent on the solubility of the particular compound in the binder-solvent used. The proportions of other constituents are as described in US. Pat.

Base

The formulations employed in this invention can beafter identical processing was 0.82.

EXAMPLE 2 A film was prepared as described in example 1 using a solution of mg of l,1-bis(4-dimethylaminophenyl) -ethylene, 50 mg of 2,6-di-t-butyl-p-cresol, 10 mg of triphenyl stibene, 200 mg of iodoform and 3 mg of 1,2-naphthoquinone in'6 cc ofa 10 percent solution of polycarbonate in '3:1 methylene chlorobenzene. Exposure and'processing as described in Example 1 produced a net D (read through a 366.0 nm filter) of 2.51. The same film without 1,2- naphthoquinone produced only a net D of 1.05'.

EXAMPLE 3 To 6 cc of a '10 percent solution of polyvir'iylbutyral in 3:1 methylene chloride-chlorobenzene was added- 130 mg of l,1-bis(4 dimethylaminophenyl)-ethylene,

50 mg of 2,6-di-t-butyl-p-cresol, 10 mg of triphenyl stibene, 280 mg of iodoform and 3 mg of 1,2-

naphthoquinone. This solution was cast as a film-upon a polyester substrate and allowed to dry. Exposure of i 360 mj/cm and fixing as described in Example] gave a net D (366.0 nm filter) of 2.70 while a filmmade without 1,2-naphthoquinone gave a net D,,',,,, of 0:46.

Nos.

EXAMPLES 4-8 A film was prepared from a solution containing 1 mg of l,l-bis(4-dimethylaminophenyl)-ethylene, 500

mg of carbon tetrabromide, 50mg of 2,6-di-t-butyl-pcresol, 10 mg of triphenyl stibene and l00 mg of trieth- -..ylamine in 6 cc of a 10% solution of polystyrene in 3:2

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 'toluene methyl ethyl ketone. This film was exposed and fixed as described in Example 1. Identical films were then prepared, except that each contained one compound representative of the materials useful for wash as described in the patents noted chloridecessed identically. The maximum density-oven base plus fog was read for each film through .both. a visible filter and a 366 nm filter. The data thus obtained are A film was cast from'a solution containing 70 mg of shown in Table 1. Examination of the data shown in 5 is(4- im t yla n ph y thyl n 50 mg of Table I will illustrate the usefulness of these additives 2.6- y -p- 0 g of triphenyl Stibene. 0 for the production of see-through masks, since the ulmg of iOdOfOrm, 100 mg of ri thylamine and 6 cc of traviolet holdback has been significantly improved with percent polystyrene in 3:2 toluene methyl ethyl kelittle or no enhancement of visible imagery. tone. This filmwascxpos ed to a medium pressure merv 0 cury arc lamp and given an exposure of 360 mj/cm EXAMPLE 9 V ,i The film was fixed by heating to 160C for 2 minutes A film was cast on polyethylene terephthalate from and the net Dnm W11S read gh 8 366-0 nm filter a solution consisting of 30 mgof 1,1-bis(4-dimeand a visible filter. Identical films were then prepared. thylaminophenyl)-ethylene, 100 mg of Z-mercaptobenexcept that each contained one compound representazothiazole, 35 mg of carbon tetrabromid 64 mg f tri, 15 tive of the materials useful for thisinvention, and these ethylamine, l cc of acetone and 6 cc of 18 percent polfilms were exposed and processed identically. Table 11 ystyrene in 2:1 toluene-ethylene dichloride. The film describes the results obtained. It should be noted that was dried at room temperature for 10 minutes and then m ny of t fil s described in Table gave an. in was exposed to a General Electric Sunl ampfThe dencreased density of 366 nm without proportionateinsity thus produced was 0.10 over base plus fog when crease in visible density, so that these "compositions read with a visible filter and the valueobtained when would beespecially suitable for the production of seeread through a 366 nm filter was 0.55 overbase plus through'rnasks. fog. An otherwise identical film was prepared,..except g I that 100 mg of phenoxazine was added to the coating i I EXAMPLE 33 solution. This film gave 0.34 net-density (visible) and v g V r, 1.07 net density at 366 nm. A film was prepared from a solution of mg of 1,1- TABLE bis(4-di nethylaminophenyl )-ethylene, 50 mg of 2,6-dit-but'yl-p cresol, lOO mg of 4-nitrobenzenesulfonyl Effect of Additives on Optical Density of Films chlondgz tn'ethylanignle f Containing Carbon Tetrabromide as Activator 3'0 ty n 1 t uene y ene d tjter Example H Amount p1 ninr dry ngat room temperature for 10 minutes, the film Addmve (mg) 66 nm) was exposed to a sunlamp to give 0.14 net density (visi- Control None (1.74 .1 0.98- ble) and 0.60 net density 366 nm). An otherwise iden- 4 Acridinc 100 0.84 2.25 5 Phenmhiuzinc )0 L05 2J4 t cal film was prepared, except that mg of phenoxa 6 l,2- Naphthoquinone 10 0.46 1 5 zine was added to the coating solution. This film pro- 7 Acnflfln duced 0.16 net density (visible) and 0.84 net density 8 N-Vmylcarbazole 0.29 2.16

TABLE II Effect of Additives on Optical Density of Films Containing lodoform as Activator Example Amount net DH, net D No. Additive (mg) (Visible) (366 nm) Control None 2.03 1.54 10 Benzoflavine 10 2.38 1.62 1 1 Carbazole 10 2.34 1.73 12 N-Vinylcarbazole 100 1.03 2.79 13 Acridan 100 0.44 1.77 14 Acridine 100 1.50 2.20 15 1-Amino-4-hydroxy-9, 1 O-anthraquinone 10 1.95 2.00 16 1,4-Diamino-9,10-anthraquinone 10 2.28 1.90 17 1-Amino-4-benzamido-9,10-anthraquinone 100 2.17 2.02 18 1,4-Diamino-2,3-dichloro-9, 1 O-anthraquinone 10 2.50 1.73 19 1 ,4-Dihydroxy-9,10-anthraquinone 10 2.31 1.71 20 2-Amino-1.4-naphthoquinone 10 2.25 2.14 21 2-Hydroxy-3-naphthoic acid anilide 10 2.66 1.68 22 2-Hydroxycarbazole-3-carboxylic acid p-chloroanilide 10 2.88 2.36 23 2-Hydroxy-a-benzocarbazole-3-carboxylic acid p-methoxyanilide 10 2.45 1.68 24 Phenoxazine 100 1.70 2.02 25 Phenothiazine 100 1.56 1.82 26 Acetanilide 100 1.83 1.60 27 Phenyl acetate 100 2.21 1.74 28 N-Acetyl-N'-phenylhydrazine 10 2.70 1.92 29 1,2.4-Benzenetriol 10 2.58 2.16 30 1,4,9.l0-Tetrahydroxy-9,10-dihydroanthracene 10 0.92 2.64 31 2.3-Dichloro-1,4-naphthoquinone 10 2.01 2.20 32 3 2.13 2.74

1,2-Naphthoquinone We claim: 1. In a non-silver photosensitive composition comprising: (l) at least one color forming compound represented by the general formula wherein each of R and R is a monovalentradical represented by the formula in which Z is selected from the group consisting of phenyl, naphthyl, and diphenyl and each of A and B is selected from the group consisting of H and alkyl; and each of R and R is selected from the group consisting of H, alkyl and aryl; and V V 2. at least one activator for said color forming compound, said activator being selected from the group the improvement 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 heterocyclic compounds selected from the group consisting of acridine, phenothiazine, acridan. carbazole, N- vinylcarbazole, and benzolflavine; quinone cornpounds selected from the group consisting of naphthoquinones and 9,10 anthraquinones; and multifunctional aromatic hydroxy compounds selected from the group consisting of 12.4- trihydroxybenzene and L49, 1 O-tetrahydroxy- 9,10-dihydroanthracene. 2. The composition of claim 1 in which the relative proportions of said color forming ethylene compound and said compound producing imagery having improved U.V. holdback is between 50:1 and 1:2.

3."The composition of claim 1 in which the color forming compound is' l 1 -bis( 4-dimethyl'aminophenyl cthyl'ene and the ultraviolet holdback compound is a quinone.

4. The composition of claim 3 wherein the quinone is a naphthoquinone. I 5. The composition of claim 4 in which thenaphthoquinone is l,2-naphthoquinone.

6. A photosensitive member comprising a support and a coating therein comprising the composition of claim 1.

7. The composition of claim 1 wherein the U.V. hold- I back compound is acridine.

Claims (11)

1. IN A NON-SILVER PHOTOSENSITIVE COMPOSITION COMPRISING: (1) AT LEAST ONE COLOR FORMING COMPOUND REPRESENTED BY THE GENERAL FORMULA

2. The composition of claim 1 in which the relative proportions of said color forming ethylene compound and said compound producing imagery having improved U.V. holdback is between 50:1 and 1:2.

2. at least one activator for said color forming compound, said activator being selected from the group consisting of (a) organic halogen compounds represented by the general formula Q-C-Hal3 wherein Q is selected from the group consisting of H, Cl, Br, I, alkyl, substituted alkyl, aryl, substituted aryl, aroyl, and arylalkyl; and each Hal represents a halogen atom selected from the group consisting of Cl, Br or I; (b) sulfur containing compounds represented by either R-SH or R-S-S-R wherein each R represents an aryl or heterocyclic ring; and (c) compounds containing both halogen and sulfur selected from the group consisting of sulfonyl and sulfenyl halides; the improvement 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 heterocyclic compounds selected from the group consisting of acridine, phenothiazine, acridan, carbazole, N-vinylcarbazole, and benzolflavine; quinone compounds selected from the group consisting of naphthoquinones and 9,10 anthraquinones; and multifunctional aromatic hydroxy compounds selected from the group consisting of 1,2,4-trihydroxybenzene and 1,4,9,10-tetrahydroxy-9,10-dihydroanthracene.

2. AT LEAST ONE ACTIVATOR FOR SAID COLOR FORMING COMPOUND SAID ACTIVATOR BEING SELECTED FROM THE GROUP CONSISTING OF (A) ORGANIC HALOGEN COMPOUNDS REPRESENTED BY THE GENERAL FORMULA Q-C-HAL3 WHEREIN Q IS SELECTED FROM THE GROUP CONSISTING OF H, CL, BR, L, ALKYL, SUBSTITUTED ALKYL, ARYL, SUBSTITUTED ARYL, AROYL, AND ARYLALKYL, AND EACH HAL REPRESENTS A HALOGEN ATOM SELECTED FROM THE GROUP CONSISTING OF CL, BR OR I, (B) SULFUR CONTAINING COMPOUNDS REPRESENTED BY EITHER R-SH OR R-S-S-R WHEREIN EACH R REPRESENTS AN ARYL OR HETEROCYCLIC RING, AND (C) COMPOUNDS CONTAINING BOTH HALOGEN AND SULFUR SELECTED FROM THE GROUP CONSISTING OF SULFONYL AND SULFENYL HALIDES THE IMPROVEMENT WHICH CONSISTS IN THE INCORPORTION 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 HETEROCYCLIC COMPOUNDS SELECTED FROM THE GROUP CONSISTING OF ACRIDINE, PHENOTHIAZINE, ACRIDAN, CARBAZOLE, N-VINYLCARBAZOLE, AND BENZOLFLAVINE, QUINONE COMPOUNDS SELECTED FROM THE GROUP CONSISTING OF NAPHTHOQUINONES AND 9,10 ANTHRAQUINONES, AND MULTIFUNCTIONAL AROMATIC HYDROXY COMPOUNDS SELECTED FROM THE GROUP CONSISTING OF 1,2,4-TRIHYDROXYBENZENE AND 1,4,9.10-TETRAHYDROXY-9,10-DIHYDROAANTHRACENE.

3. The composition of claim 1 in which the color forming compound is 1,1-bis(4-dimethylaminophenyl)-ethylene and the ultraviolet holdback compound is a quinone.

4. The composition of claim 3 wherein the quinone is a naphthoquinone.

5. The composition of claim 4 in which the naphthoquinone is 1, 2-naphthoquinone.

6. A photosensitive member comprising a support and a coating therein comprising the composition of claim 1.

7. The composition of claim 1 wherein the U.V. hold-back compound is acridan.

8. The composition of claim 1 wherein the U.V. hold-back compound is an anthraquinone.

9. The composition of claim 1 wherein the U.V. hold-back compound is acridine.