US3350204A - Colloid transfer process utilizing an oil-soluble u. v. absorber - Google Patents

Description

nite tates 3,350,204 COLLOID TRANSFER PROCESS UTKLIZENG AN OIL-SOLUBLE U.V. ABSORBER James G. Smith and Thomas I. Abbott, Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Mar. 13, 1964, Ser. No. 351,846

Claims. (Cl. 96-28) ABSTRACT OF THE DISCLOSURE This invention relates to photography and particularly to a transfer process of printing a photographic image.

In U.S. Patent No. 2,596,756, Yutzy and Yackel describe a colloid transfer process in which a tanning developer incorporated in an unhardened emulsion layer results in tanning the gelatin in the exposed areas. The pig mented unexposed and untanned areas are transferred to the receiving sheet to provide a positive image.

It has been customary in the colloid transfer process to maintain temperature control of the bath for the activator at about 82 F. by using processing equipment having a thermostatic controlled reservoir for the activator. When the temperature becomes elevated due to higher room temperature or the like, there is often a noticeable difference in the resulting print. For instance, a much lower density is obtained. For this reason, it has been desirable to find a means of providing temperature latitude for the colloid transfer process so that the exposed emulsion can be processed at room temperatures as high as 85 F. and, at the same time, to attain the same degree of quality as is now attained using the temperature controlled conditions.

Light sensitive emulsions useful in the colloid transfer system have light sensitivity levels which are fast enough for imagewise exposure in suitable exposing equipment using incandescent lamps, but slow enough so that overall exposure will not occur when handled in average office room light, such as fluorescent light, rich in blue light. However, it has been desirable to increase the speed of exposure in the copying equipment without decreasing-the tolerance to room light, and preferably even to increase the tolerance to room light. However, efforts to increase the emulsion sensitivity to imagewise exposure have usually also resulted in a corresponding increase in room light sensitivity of the element.

Attempts have 'been made to incorporate agents into photographic emulsions which would filter out certain areas of the light spectrum and these have been somewhat successful with ordinary photographic emulsions. A large number of ultraviolet absorbers have been proposed for this use.

Ultraviolet absorbing compounds for photographic use must generally have good compatibility with the medium in which they are incorporated, be inert to other photographic addenda in the element and in the processing solution, must have good ultraviolet absorptivity and be stable to ultraviolet radiation. Representative compounds for incorporation in photographic elements are described for 3,350,204 Patented Oct. 31 1 967 example, in U.S. Patent 2,685,512, issued Aug. 3, 1954; U.S. Patent 2,739,888, issued Mar. 27, 1956; U.S. Patent 2,719,086, issued Sept 27, 1955; U.S. Patent 2,739,971, issued Mar. 27, 1956; U.S. Patent 2,747,996, issued May 29, 1956, and U.S. Patent 2,784,087, issued Mar. 5, 1957.

A typical procedure for forming finely-divided particulate dispersions and avoiding unwanted crystallization or other aggregation of particles is the so-called Fischer method in which a nondiffusing compound is provided with a sulfonic acid or other solubilizing group so that it can be dissolved in water as the alkali metal salt and the solution are added to the aqueous gelatin coating composition.

The Fischer method is convenient for incorporating ultraviolet absorbers in finely-divided and uniformly dispersed form and the resulting ultraviolet absorbing layers have shown good long-term stability.

Another technique employed in incorporating ultraviolet absorbing compounds into gelatin layers is by dissolving the absorber in a polar solvent, e.g., water and/ or methanol, and then bathing the photographic gelatin coating in this solution. A typical example of this method is disclosed in U.S. Patents 2,685,512, 2,719,086, 2,747,996 and 2,808,330.

Another method for incorporating compounds in finelydivided, noncrystallized form is the solvent-dispersion technique in which the nondiffusing compound is dissolved in an organic solvent and the resulting solution is intimately blended in an aqueous gelatin solution. This technique as applied to couplers is described, for example, in U.S. Patents 2,322,027, issued June 15, 1943, 2,801,170 and 2,801,171, both issued July 30, 1957; 2,870,012, issued Jan. 20, 1959, and 2,991,177, issued July 4, 1961.

A typical example of the use of the solvent dispersion technique as applied to ultraviolet absorbers is described in U.S. Patent 2,739,888, issued Mar. 27, 1961.

Incorporation of ultraviolet absorbers into the colloid transfer emulsion presents additional problems because the unhardened photographic emulsions used in the colloid transfer processes, e.g., as described in U.S. Patent 2,596,- 756, also normally contain a tanning developer dispersion. When aqueous solutions of known ultraviolet light absorbers in useful concentrations are incorporated in such emulsions, the emulsions coagulate and cannot be used in the colloid transfer process.

Therefore, there has been a serious problem in finding an ultraviolet absorber which could be incorporated into the emulsion which would be compatible with the incorporated developers and which would be stable after incorporation. In addition, there has been the problem of increasing the processing temperature latitude of the emulsion.

We have discovered a means of decreasing the sensitivity of the element to room light without decreasing the sensitivity of the emulsion to imagewise exposure in the copying device. Moreover, we have discovered a. means of increasing the processing temperature latitude. These improvements are attained by use of a particular system of incorporating in the emulsion certain ultraviolet absorbing agents which do not adversely affect the emulsion.

One object of this invention is to increase the temperature latitude for developing an unhardened emulsion containing a tanning developer. Another object is to decrease the room light sensitivity of an unhardened, tanning developer containing light sensitive silver halide emulsion. A further object is to improve the senstivity of a colloid transfer emulsion to the imagewise exposure in an exposure device without increasing room light sensitivity. A further object is to provide addenda for colloid transfer photographic emulsions which screen out ultraviolet light, but which do no adversely affect the emulsion.

The above objects are attained by incorporating an ultraviolet absorber soluble in a crystalloidal solvent in an unhardened gelatino-silver halide emulsion containing a dihydroxybenzene tanning developing agent.

In our preferred embodiment, at least one ultra-violet absorber, such as -benzylidene-3-cetyl-2-phenylimino-4- thiazolidone is dissolved in a crystalloidal solvent, such as, for example, tricresyl phosphate, along with the tanning developing agent. This solution is added to a light sensitive gelatino-silver chloride emulsion along with spectral sensitizing dyes and coatings aids for coating on a paper support. After exposure to light, the emulsion is processed in an alkaline activator and contacted against the receiving sheet. The emulsion is tanned in the exposed areas and the unexposed areas comprising untanned gelatin and transferred to the receiving sheet to form a positive image.

Other ultraviolet absorbers which are operative in our invention include 5-(4-methoxy 3-sulfo)benzylidene-2- phenylirnino-3-n-octylthiazolidone, sodium salt, 2-(2-hydroxy 3,5-di-tert-amylphenyl)benzotriazole, etc. If desired, a combination of two or more of these agents may be used.

In the silver halide emulsion, we prefer to use l0-l00 grams absorber (or combined absorbers) per mole of silver halide. Sufficient high boiling water insoluble crystalloidal material is used to dissolve the ultraviolet absorber. Typical crystalloidal materials are described in U.'S. Patent 2,322,027 issued to Jelley et al., June 15, 1943, incorporated herein by reference.

Small amounts of an aqueous solution of a soluble ultraviolet absorber may be incorporated in the emulsion in amounts insufficient to coagulate the emulsion. However, the amounts of the aqueous solution of ultraviolet absorber which can be tolerated by the emulsion are not enough to be effective in providing a significant room light handling improvement in the colloid transfer type photographic element. Therefore, the combination of a non-coagulating amount of the aqueous ultraviolet absorber along with suflicien-t oil soluble absorber may be used to obtain a desired overall effect rather than obtaining the desired effect by using only oil soluble ultraviolet absorbers.

The silver halide emulsion used in the sensitive element of our invention may be ordinary unsensitized gelatino- 1 silver halide emulsion, or an optically sensitized or chem- 0 ically sensitized emulsion, in which the gelatin is substantially unhardened. The emulsion may contain a substantially non-diffusing developing agent of the type as disclosed in Yackel US. Patent No. 2,592,368 and if desired, the emulsion may also contain a non-tanning, substantially non-diffusing developing agent as described in Yutzy and Yackel US. Patent No. 2,716,059.

If the developing agent is incorporated in the emulsion layer, the solution used to effect development may be a simple alkaline solution such as a sodium carbonate or a sodium hydroxide solution.

The following examples are intended to illustrate our invention but not to limit it in any way.

EXAMPLE 1 To 100 grams (0.28 mole) of a fine-grain silver chloride gelatin emulsion at 40 C. the following were added:

(A) 22 grams of Dispersion A 1 (B) Spectral sensitizing dyes (C) 7 grams of a 15.2% aqueous saponin solution 1 Dispersion A: (1) 14 grams of a 10% aqueous gelatin solution 1.4 grams of a 7.6% aqueous saponin soltion Disperse at 40 C. (2)

1, and pass through colloid mill.

This mixture was coated on a paper base and dried. The dried coating and a similar coating without S-benzylidened-cetyl-2-phenylimino-4-thiazolidone in Dispersion A were partially covered with an ultraviolet filter (Wratten No. 2B) and were exposed through a steptablet to an incandescent lamp. The coatings were processed in 4% K CO activator and the unhardened image transferred to a Water absorbent receiving sheet. Exposure through a Wratten No. 2B filter caused an 0.15 log E speed change on the coating containing 5-benzylidene-3- cotyl-2-phenylimino-4-thiazolidone and over an 0.45 log E speed change on a check coating without 5-benzylidene- 3-cetyl-2-phenylimino-4-thiazolidone. Exposure through a Wratten No. 2B filter caused an 0.15 log E speed change on the coating Without Dispersion A if exposed through the support.

EXAMPLE 2 To grams of a fine-grain silver chloride gelatin emulsion at 40 C. the following were added:

(A) 19.6 grams Dispersion B 2 (B) 3.75 grams Dispersion C (C) Spectral sensitizing dyes (D) 7 cc. of a 15.2% saponin solution This mixture was coated onto a paper support and dried. The dried coating and a similar coating without Dispersion C were flashed with light from fluorescent tubes (70 ft. candles illumination) before image exposure. The transferred image from the coating without Dispersion C was affected with more than 10-second flash exposure before image exposure while the coating containing Dispersion C could be flashed for 30 seconds before image exposure without affecting the transferred image.

EXAMPLE 3 To 100 grams of a fine grain silver chloride gelatin emulsion at 40 C. the following were added:

(A) Spectral sensitizing dyes (B) 7 grams of a 15.2% aqueous solution of saponin (C) 1.1 grams of 5-(4-methoxy-3-sulfo)benzylidene-Z- phenylimino3-n-octylthiazolidone, sodium salt, dissolved in water.

Addition of the aqueous solution of the ultraviolet absorber resulted in coagulation of the emulsion so that it could not be coated.

EXAMPLE 4 To the same emulsion described in Example 3 was added the same amount of saponin and the same sensitizing dyes, after which was added 0.34 gram of 2,5- bis[2 methoxy-x-sulfophenyl]thiazolo[5,4-d]thiazole disodium salt dihydrate, in sufficient water to dissolve. The emulsion coagulated and could not be coated.

EXAMPLE 5 To 100 grams of a fine-grain silver chloride gelatin emulsion at 40 C. the following were added:

(A) 19.6 grams Dispersion B 2 (B) 28 cc. of a 2% aqueous solution 5-(4-methoxy-3- sulfo)benzylidene 2-phenylimino-3-n-octylthiazolidone, sodium salt 2 Dispersion B 14 grams of a 10% aqueous gelatin solution 1.4 grams of a 7.6% aqueous saponin solution Disperse at 40 C. (2)

2.8 gnams tricresyl phosphate 1.0 gram 4 phenyl catechol 0.4 gram 4 methoxynaphthol Dissolve at 0., add 2 to 1, and pass through colloid mill.

= Dispersion C (1) Disperse 100 cc. of a. 10% aqueous gelatin solution and 5 cc. tri-isopropyl naphthalene sulfonate.

(2) Dissolve 10 grams 2-(2-hydroxy-3,o-di-tert-amylphengl)- benzotri azole in 20 cc. B-butoxy-B-ethoxy acetate, add to 1, and pass through colloid mill, chill set, noodle, and wash 6 hours; weight after washing grams.

(C) Spectral sensitizing dyes (D) 7 grams of a 15.2% aqueous solution of saponin EXAMPLE 6 To 100 grams of a fine-grain silver chloride gelatino emulsion at 40 C. the following were added:

(A) 20.1 grams of Dispersion D 4 (B) 28 cc. of a 2% aqueous solution of 5-(4-methoxy-3- sulfo benzylidene-Z-phenylimino-3 -n-octylthiazolidone, sodium salt (C) Suitable sensitzing dyes (D) 7 grams of a 15.2% aqueous solution of saponin This mixture was coated onto a paper support and dried. The dried coating was compared to a similar coating without 5-benzylidene-3-cetyl-2-phenylimino-4-thiazolidone in Dispersion D and 5-(4-methoxy-3-sulfo)benzylidene-Z- pnenylimino-3-n-octylthiazolidone, sodium salt using the technique described in Example 1. Exposure through a Wratten No. 2B filter caused an 0.15 log E speed change on the coating containing Dispersion D+5-(4-rnethoxy-3- sulfo)benzylidene 2 phenylimino-3-n-octylthiazolidone, sodium salt and an 0.45 log E speed change on the coating without these additions.

EXAMPLE 7 An emulsion similar to that described in Example 1 was prepared. This emulsion was coated on a paper support which had a clear high density polyethylene layer on the back and a pigmented low density polyethylene layer on the face. A polyethylene paper stock was electron bombarded before emulsion coating. The emulsion was coated to yield a coverage of 100 milligrams of silver per square foot, 175 grams of gelatin per square foot and 258 milligrams of 5-benzylidene-3-cetyl-2-phenylimino-4 thiazolidone per square foot. The thiazolidone was added as a Dispersion A as described in Example 1. This coating was identified as A. A coating simlar to (A) was made except that the thiazolidone was omitted. Coatings A and B were exposed and developed in an activator at various temperatures from 7085 F. The activator was an alkaline solution having a pH of about 9.4. The following results were obtained:

Where we refer to a unhardened gelatin emulsion layer, we mean a layer that is not harder than would be the case with gelatin containing 0.25 ounce of formalde- 4 Dispersion D:

14 gnams of a aqueous gelatin solution 1.4 grams of a 7.6% aqueous solution of saponin Disperse at 40 C. (2)

2.8 grams of tricresylphosphate 1.0 gram 4 phenyl ca-techol 0.4 gram 4 methoxynanhthol 4 0.5 gram 5-benzyli-dene3cetyl-2-phenylim1no-4-th1az0l1done Dissolve at 110 0., add 2 to 1, and pass through colloid mill.

6 hyde (40 percent, diluted 1 to 3 with water) per pound of gelatin when freshly coated, or 0.1 ounce of the formaldehyde solution per pound of gelatin for a sample aged 3 to 6 months.

It will be understood that the modifications and equivalents included herein are by way of example only and that our invention is to be taken as limited only by the scope of the appended claims.

We claim 1. A photographic element having thereon an unhardened colloidal silver halide emulsion containing a dihydroxybenzene developing agent and an oil soluble ultraviolet absorber dissolved in a substantially water insoluble, low molecular weight, organic crystalloidal material having a boiling point above about C.

2. A photographic element having thereon an unhardened colloidal silver halide emulsion containing a dihydroxybenzene developing agent and an oil soluble ultraviolet absorber selected from the class consisting of the sodium salt of 5-(4-methoxy-3-sulfo)benzylidene-Z- phenylimino-3-n-octylthiazolidone, 2-(2-hydroxy-3,5-ditert-amylphenyl)benzotriazole and 5-benzylidene-3-cetyl- 2-phenylimino-4-thiazolidone.

3. A photographic element having thereon an unhardened colloidal silver halide emulsion containing a dihydroxybenzene developing agent and the sodium salt of 5 (4 methoxy-3-sulfo)benzylidene-Z-phenylimino-3- octylthiazolidone, dissolved in a substantially water insoluble, low molecular weight, organic crystalloidal material having a boiling point above about 175 C.

4. A photographic element having thereon an unhardened colloidal silver halide emulsion containing a dihydroxybenzene developing agent and 2-(2-hydroxy-3,5- 'di-tert-amylphenyl)-benzotriazole dissolved in a substantially water insoluble, low molecular weight, organic crystalloidal material having a boiling point above about 175 C.

5. A photographic element having thereon an unhardened colloidal silver halide emulsion containing a dihydroxybenzene developing agent and 5-benzylidene-3cetyl- 2-phenylimino-4-thiazolidone dissolved in a substantially water insoluble, low molecular weight, organic crystalloidal material having a boiling point above about 175 C.

6. A photographic element having thereon an unhardened colloidal silver halide emulsion containing a dihydroxybenzene developing agent, a non-tanning developing agent and an oil soluble ultraviolet absorber dissolved in a substantially water insoluble, low molecular Weight, organic crystalloidal material having a boiling point above about 175 C.

7. A photographic element having thereon an unhardened colloidal silver halide emulsion containing a dihydroxybenzene developing agent, a non-tanning developing agent and an oil soluble ultraviolet absorber selected from the class consisting of the sodium salt of 5-(4- methoxy 3-sulfo)benzylidene-Z-phenyliminc-3-n-octylthiazolidone, 2- 2-hydroxy-3,S-di-tert-amylphenyl -benzotriazole and 5-benzylidene-3-cetyl-2-phenylimino-4-thiazolidone dissolved in a substantially water insoluble, low molecular weight, organic crystalloidal material having a boiling point above about 175 C.

8. A photographic element having thereon an unhardened colloidal silver halide emulsion containing a dihydroxybenzene developing agent, a non-tanning developing agent and the sodium salt of 5-(4-methoxy-3-sulfo) benzylidene 2 phenylimino 3-n-octylthiazolidone, dissolved in a substantially water insoluble, low molecular weight, organic crystalloidal material having a boiling point above about 175 C.

9. A photographic element having thereon an unhardened colloidal silver halide emulsion containing a dihydroxybenzene developing agent, a non-tanning developing agent and 2-(2-hydroxy-3,S-di-tert-amylphenyl)-benzotriazole, dissolved in a substantially water insoluble, low

molecular weight, organic crystalloidal material having a boiling point above about 175 C.

10. A photographic element having thereon an unhardened colloidal silver halide emulsion containing a dihydroxybenzene developing agent, a non-tanning developing agent and -bcnzylidene-3-cetyl-2-phenylimino- 4-thiazolidone, dissolved in a substantially water insoluble, low molecular weight, organic crystalloidal material having a boiling point above about 175 C.

11. The method of photographic reproduction which comprises exposing to a subject a photographic element having thereon an unhardened colloidal silver halide emulsion containing a dihydroxybenzene developing agent and an oil soluble ultraviolet absorber dissolved in a substantially water insoluble, low molecular weight, organic crystalloidal material having a boiling point above about 175 (1., developing said exposed emulsion layer with an alkaline activator solution and transferring the unhardened areas of said colloid layer to an absorbent support.

12. The method of photographic reproduction which comprises exposing to a subject a photographic element having thereon an unhardened colloidal silver halide emulsion containing a dihydroxybenzene developing agent and an oil soluble ultraviolet absorber selected from the class consisting of the sodium salt of 5-(4-methoxy-3- sulfo benzylidene-2-phenylimino-3 -n-octylthiazolidone, 2- (2-hydroxy-3,S-di-tert-amylphenyl)-benzotriazole and 5- 'benzylidene-3-cetyI-Z-phenylimino-4-thiazolidone.

13. The method of photographic reproduction which comprises exposing to a subject a photographic element having thereon an unhardened colloidal silver halide emulsion containing a dihydroxybenzene developing agent and the sodium salt of 5-(4-methoxy-3-sulfo)benzylidene- 2-phenylimino-3-octylthiazolidone, dissolved in a substantially Water insoluble, low molecular weight, organic, crystalloidal material having a boiling point above about 175 C., developing said exposed emulsion layer with an alkaline activator solution and transferring the unhardened areas of said colloid layer to an absorbent support.

14. The method of photographic reproduction which comprises exposing to a subject a photographic element having thereon an unhardened colloidal silver halide emulsion containing a dihydroxybenzene developing agent and 2 (2-hydroxy-3,S-di-tert-amylphenyl)-benzotriazole dissolved in a substantially Water insoluble, low molecular weight, organic crystalloidal material having a boiling point above about 175 C., developing said exposed emulsion layer with an alkaline activator solution and transferring the unhardened areas of said colloid layer to an absorbent support.

15. The method of photographic reproduction which comprises exposing to a subject a photographic element having thereon an unhardened colloidal silver halide emulsion containing a dihydroxybenzene developing agent and 5 benzylidene-3-cetyl-Z-phenylimino-4-thiazolidone, dissolved in a substantially water insoluble, low molecular weight, organic crystalloidal material having a boiling point above about 175 C., developing said exposed emulsion layer with an alkaline activator solution and transferring the unhardened areas of said colloid layer to an absorbent support.

16. The method of photographic reproduction which comprises exposing to a subject a photographic element having thereon an unhardened colloidal silver halide emulsion containing a dihydroxybenzene developing agent, a

non-tanning developing agent, and an oil soluble ultraviolet absorber dissolved in a substantially water insoluble, low molecular weight, organic crystalloidal material having a boiling point above about C., developing said exposed emulsion layer with an alkaline activator solution and transferring the unhardened areas of said colloid layer to an absorbent support.

17. The method of photographic reproduction which comprises exposing to a subject a photographic element having thereon an unhardened colloidal silver halide emulsion containing a dihydroxybenzene developing agent, a non-tanning developing agent and an oil soluble ultraviolet absorber selected from the class consisting of the sodium salt of 5-(4-methoxy-3-sulfo)-benzylidene-2- phenylimino-3-n-octylthiazolidone, 2(2-hydroxy-3,5-ditert amylphenyl) benzotriazole and 5-benzylidene-3- cetyl-2-phenylimino-4-thiazolidone, dissolved in a substantially water insoluble, low molecular weight, organic cryst-alloidal material having a boiling point above about 175 C., developing said exposed emulsion layer with an alkaline activator solution and transferring the unhardened areas of said colloid layer to an absorbent support.

18. The method of photographic reproduction which comprises exposing to a subject a photographic element having thereon an unhardened colloidal silver halide emulsion containing a dihydroxybenzene developing agent, a non-tanning developing agent and the sodium salt of 5- (4 methoxy-3-sulfo)benzylidene-Z-phenylimino-3-octylthiazolidone dissolved in a substantially water insoluble, low molecular weight, organic crystalloidal material having a boiling point above about 175 C., developing said exposed emulsion layer with an alkaline activator solution and transferring the unhardened areas of said colloid layer to an absorbent support.

19. The method of photographic reproduction which comprises exposing to a subject a photographic element having thereon an unhardened colloidal silver halide emulsion containing a dihydroxybenzene developing agent, a non-tanning developing agent and 2-(2-hydroxy-3,5- di-tert-amylphenyl)-benzotriazole dissolved in a substantially water insoluble, low molecular weight, organic crystalloidal material having a boiling point above about 175 0, developing said exposed emulsion layer with an alkaline activator solution and transferring the unhardened areas of said colloid layer to an absorbent support.

20. The method of photographic reproduction which comprises exposing to a subject a photographic element having thereon an unhardened colloidal silver halide emulsion containing a dihydroxybenzene developing agent, a non-tanning developing agent and 5-benZylidene-3-cetyl- 2-phenylimino-4-thiazolidone, dissolved in a substantially water insoluble, low molecular weight, organic crystalloidal material having a boiling point above about 175 C., developing said exposed emulsion layer with an alkaline activator solution and transferring the unhardened areas of said colloid layer to an absorbent support.

References Cited UNITED STATES PATENTS 2,607,684 8/1952 Novak et al. 96-84 NORMAN G. TORCHIN, Primary Examiner.

I. H. RAUBITSCH'EK, Assistant Examiner.

Claims (2)

1. A PHOTOGRAPHIC ELEMENT HAVING THEREON AN UNHARDENED COLLOIDAL SILVER HALIDE EMULSION CONTAINING A DIHYDROXYBENZENE DEVELOPING AGENT AND AN OIL SOLUBLE ULTRAVIOLET ABSORBER DISSOLVED IN A SUBSTANTIALLY WATER INSOLUBLE, LOW MOLECULAR WEIGHT, ORGANIC CRYSTALLOIDAL MATERIAL HAVING A BOILING POINT ABOVE ABOUT 175*C.

11. THE METHOD OF PHOTOGRAPHIC REPRODUCTION WHICH COMPRISES EXPOSING TO A SUBJECT A PHOTOGRAPHIC ELEMENT HAVING THEREON AN UNHARDENED COLLOIDAL SILVER HALIDE EMULSION CONTAINING A DIHYDROXYBENZENE DEVELOPING AGENT AND AN OIL SOLUBLE ULTRAVIOLET ABSORBER DISSOLVED IN A SUBSTANTIALLY WATER INSOLUBLE, LOW MOLECULAR WEIGHT, ORGANIC CRYSTALLOIDAL MATERIAL HAVING A BOILING POINT ABOVE ABOUT 175*C., DEVELOPING SAID EXPOSED EMULSION LAYER WITH AN ALKALINE ACTIVATOR SOLUTION AND TRANSFERRING THE UNHARDENED AREAS OF SAID COLLOID LAYER TO AN ABSORBENT SUPPORT.