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Publication numberUS3642479 A
Publication typeGrant
Publication dateFeb 15, 1972
Filing dateMar 2, 1970
Priority dateMar 2, 1970
Also published asCA969411A, CA969411A1
Publication numberUS 3642479 A, US 3642479A, US-A-3642479, US3642479 A, US3642479A
InventorsJames A Van Allan, Dennis E De Meyer, Frank D Allen
Original AssigneeEastman Kodak Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Photographic element and process
US 3642479 A
Abstract
Photographic elements having a support on which is coated a layer including a light-sensitive halocarbon and a 1,4-pyran derivative like 1-(p-N,N-dimethylaminophenyl)-1H-3-(p-ethoxyphenyl)naphtho[2,1-b]pyran or 4-(p-N,N-dimethylaminophenyl)-2-phenyl-4H-1-benzo[b]pyran yield printout images in exposed areas on exposure to actinic rays. The resultant printout image can be intensified by heating.
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Description  (OCR text may contain errors)

United States Patent Van Allan et al.

[451 Feb. 15, 1972 [54] PHOTOGRAPHIC ELEMENT AND PROCESS [72] Inventors: James A. Van Allan; Dennis E. De Meyer, both of Rochester, N.Y.; Frank D. Allen,

, deceased, late of Rochester, NY.

[73] Assignee: Eastman Kodak Company, Rochester,

[22] Filed: Mar. 2, 1970 211 Appl. No.: 15,867

[52] US. Cl ..96/48 R, 96/90, 96/90 PC [51] Int. Cl. 5/24, G036 1/72 I 58] Field of Search ..96/90, 90 PC, 48

I56] References Cited UNITED STATES PATENTS 3,486,899 l2/l969 Brown ..96/90 3,121,633 2/1964 Sprague et a]. ..96/90 3,532,638 10/1970 Otis ..96/90 PC X Primary Examiner-Norman G. Torchin Assistant ExaminerRichard E. Fichter AttorneyW. H. J. Kline, J. R. Frederick and D. M. De Leo [57] ABSTRACT The resultant printout image can be intensified by heating.

9 Claims, No Drawings PHOTOGRAPHIC ELEMENT AND PROCESS This invention relates to photography and particularly to photographic elements and processes for forming printout images.

It is known that certain halocarbons and polyhalocarbons are light sensitive and yield photographic products which are capable of producing colored materials from such colorless materials as certain dyes, and diarylamines. Examples of this light sensitivity can be found in Mechanisms and Structures In Organic Reaction, Gould, page 744; and in U.S. Pat. Nos. 3,102,810 and 3,121,633; in British Pat. Nos. 916,779 and 719,919. These references are based on the photoreaction of polyhalocarbons with leuco dyes to yield the corresponding colored forms of the dyes.

While polyhalocarbons havingbeen employed separately as light-sensitive addenda for certain photographic processes and elements. They have not been combined with 4H-pyran derivatives to prepare photographic printout elements.

Accordingly, an object of this invention is to provide novel photographic elements. 7

Another object of this invention is to provide new photographic elements useful in preparing printout images.

Still another object of the present invention is to provide novel photographic elements including, as the image-forming components, at least one halocarbon and at least one 4H- pyran derivative.

An additional object of this invention is to provide a new photographic process for producing printout images.

Other objects and advantages of this invention will become increasingly apparent from a reading of the following specification and appended claims.

The objects of this invention are accomplished both with photographic elements wherein a support is coated with a layer including a light-sensitive halocarbon and a 4H-pyran derivative and with a photographic process for the preparation of printout images including. imagewise exposing an element such as described above to actinic rays.

4H-pyran derivatives useful in the photographic elements of this invention include those having at least one aromatic substituent on the pyran ring. Especially desirable are those substituted at the 2-position and at the 4-position, with at least one of these substituents being an aromatic radical which itself can be still additionally substituted. Additionally the pyran nucleus is desirably fused to an aromatic nucleus to form, for example, a benzopyran or a [2, l -b]naphthopyran.

Particularly advantageous pyran derivatives include those having the formula:

wherein a. each of R and R represent either a hydrogen atom, an alkyl radical or an aryl radical and at least one of R or R is an aryl radical, b. each of R and R, when taken alone, represents a hydrogen atom, and

c. R and R, when taken together, represent the atoms necessary to complete an aromatic ring system.

As defined herein, the term alkyl radical refers to straight and branched chain alkyl radicals having from one to about four carbon atoms like methyl, ethyl, 2-methoxyethyl, propyl, isopropyl, n-butyl, or the like, etc. The alkyl radical can be additionally substituted, e.g., ethoxycarbonylcyanomethyl, ethoxycarbonylbenzoylmethyl, nitromethyl, etc. Alkoxy radical refers to alkoxy radicals having from one to about four carbon atoms such as methoxy, ethoxy, propoxy, butoxy, etc., and preferably methoxy or ethoxy. The term aryl radical designates aromatic substituted or unsubstituted aryl radicals having from six to 10 carbon atoms in the nucleus, and including such aryl radicals as phenyl, naphthyl, p-tolyl, p-ethoxyphenyl, p-dimethylaminophenyl and the like. Also as used herein, the designation aromatic ring system refers to a mono or poly cyclic, carbocyclic aromatic nucleus like benzene, naphthalene, anthracene, phenanthrene, etc., which is completed by the atoms represented by R and R taken together and is fused to the parent pyran ring between the adjacent carbon atoms substituted by R and R.

Especially advantageous pyran derivatives as described herein include those wherein R represents either a hydrogen atom, a methyl radical, an N,N-dimethylaminophenyl radical or a p-methylphenylthio radical and R represents a phenyl radical including substituted phenyl radicals like p-ethox yphenyl, N,N-dimethylaminophenyl and the like. Still other especially desirable pyran compounds include those wherein R and R when taken together, represent a 1,4-buta-1,3- dienylene radical (i.e., CH=CH-CH:CH) with R and R thereby completing a benzene nucleus.

Preferred 4l-l-pyran derivatives useful in the photographic elements of this invention include TABLEl Compound l l-(p-N,N-dimethylaminophenyh-l H-3-(pethoxyphenyhnaphthol2,I-h]pyran, 2 l-(p-N,N-dimethylaminophcnyl)-lH-3- phenylnaphthol2,l-b]pyran, 3 4-(p-N,N-dimethylaminophenyl)-2-phenyl-4H-lbenzol blpyran 4 2-(p-N,N-dimethylaminophenyl)-4H-benzo[blpyran 5 lH-3-(p-N,N-dimethylaminophcnyl)naphlhol2,l-hlpyran, 6 2- hcnyl-4H-bcnzo[blpyran. 7 l-(p-mlylthio)-1H-3-(p-cthnxyphenyl)naphtho-l2,1-

blpyran. 8 2-ethoxyphenyl-4-(p-tolyllhio)-4H-benzn|blpyran, 9 l( l-ethoxycarbonyl-l-cyanomethyl)-l H-3-(pethoxyphenyUnaphlhol 2,l-b]pyran, l0 4-( l-ethoxycarbonyl-l-eyanomethyl)-2-phcnyl-4H- benzolhlpyran, ll l(l-cthoxycarbonyl-1-benzoylmcthyl)1H-3-(pethoxyphenyUnaplhoIZ. l -blpyran. and 12 l-nitromethyl-lH-3-(p-N.N-

dimethylaminophcnyl)naphthol-hlpyran.

Also included in the present photographic elements, in

combination with at least one pyran derivative like those mentioned hereinabove is at least one halocarbon or polyhalocarbon compound. The pyran derivatives and halocarbon compounds are generally combined herein in weight ratios of from about 3:1 to about 1:5 respectively, and preferably in substantially equal amounts by weight. Useful halocarbon compounds include, for example, a-halocarbonyl compounds like 01,01,04- tribromoaceto-phenone, poly(vinyl halides) such as poly(vinyl bromide) as well as perhalides and the like. Especially desirable halocarbon compounds are those known to be decomposed by exposure to actinic rays (i.e., ultraviolet and blue light) and which are not acidic. Preferred halocarbon compounds of this type include polyhalocarbons having three halogen atoms chemically bonded to a terminal carbon atom, ie, those having the formula R -C-(X) wherein X represents a halogen atom and R represents either a halogen atom, an alkyl radical, a haloalkyl radical, an aryl radical or an aroyl radical. Exemplary polyhalogens include such compounds as polyhaloalkanes like iodoform, carbon tetrabromide, pentabromoethane, hexabromoethane, hexachloroethane and tribromophenylmethane. Bromo and iodo compounds are especially preferred clue to their inherently greater light sensitivity as compared to that of the corresponding chloro compounds. Polyhalocarbons, such as iodoform,

which can be inactivated or diffused from a coated layer on heat treatment are also preferred since they permit convenient stabilization of the photographic image by the application of heat.

In addition to pyran derivatives and halocarbon compounds, the photographic elements of this invention can contain additional addenda, e.g., sensitizers or addenda to enhance storage stability or either image quality or raw stock or image stability. As an example, certain nitrogen containing compounds promote the photographic speed and resultant image density at any given exposure level. These materials are well known in the photographic art and include such compounds as 5dimethylaminocoumarin, 6-diethylamino-4- methylcoumarin, carbazole, diphenylformamide, 4- dimethylaminobenzaldehyde, phenothiazine and the like.

As well as sensitizing addenda, materials which inhibit premature reaction in the sensitive layers are useful inclusions. Presumably, such compounds, which can be included singly or in combination and admixture, function to buffer the imageforming components against a pH change, i.e., to an acidic pH, which would promote a premature printout reaction. Desirable stabilizing materials include nitrogen-containing heterocycles like benzimidazole, Z-methylbenzimidazole, 2- styrylbenzimidazole as well as related nitrogen containing compounds such as azoles like isoazole, triazole, benzotriazole, etc., azine compounds like pyrimidine, pyrazine, benzopyrimidine and other diazines or triazine compounds such as l,2,4-triazine, 1,2,3-triazine, l,3,5-triazine, etc.

Other useful addenda materials include image stabilizers, they being compounds which enhance the resistance of a resultant photographic image against deterioration from subsequent exposure to heat, light or the like energies which can cause fading or discoloration of the image. Exemplary such stabilizers include thiazine compounds like phenothiazine and oxines such as alkoxyboroxines.

Generally, the image-forming components and additional stabilizing or other modifying addenda are dispersed in a hydrophobic film-forming resin binder to promote the formation of a coated layer. Desirable resinous matrix vehicles include those which have a softening point sufficiently high to resist tackiness at the temperature ranges, i.e., up to about l50 C., useful for intensifying or stabilizing photographic images produced on elements of this invention. Additionally, the pH of the resin binder should not be such that it either promotes or unduly inhibits, i.e., more than do the described stabilizers, the image-forming reaction. Exemplary matrix vehicles, having the noted characteristics, can be selected from a wide variety of materials, including natural resins, modified natural resins and synthetic resins. Exemplary useful natural resins are balsam resins, colophony and shellac. Exemplary suitable modified natural resins are colophony-modified phenol resins and other resins listed below with a large proportion of colophony. Suitable synthetic resins include the extensive variety ofsynthetic resins, for example, polymers, such as vinyl polymers including a polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinyl acetals, polyvinyl ether and polyacrylic and polymethacrylic esters; polystyrene and substituted polystyrenes or polycondensates, e.g., polyesters, such as phthalate resin, terephthalic and isophthalic polyesters, maleinate resin and colophony-mixed esters of higher alcohols; phenol-formaldehyde resins, including colophony-modified phenol-formaldehyde condensates, aldehyde resins, ketone resins, polyamides and polyadducts, e.g., polyurethanes. Moreover, high-melting polyolefins, such as various polyethylenes, polypropylenes, polyisobutylenes and chlorinated rubber are suitable. Additional useful resinous binder materials are known to those skilled in the polymer arts.

To prepare a composite photographic element of this invention, the image-forming components and such supplemental addenda compounds as are desired are generally dissolved or dispersed in a solution of matrix vehicle to prepare a coating composition which can then be applied to a support material by solvent coating techniques. In a coating formulation, the halocarbon and pyran derivative are generally present in stoichiometric amounts or with an excess of pyran derivative. Modifying addenda, if included, can be present in widely varying amounts and the chosen amount will depend on both the selection and quantities of image-forming components as well as the modifying effect desired. Conventionally they are included in an amount of from about 1 to about 35 percent by weight of the image-forming ingredients. The image-forming compositions, including stabilizers or other modifying addenda are generally incorporated into a coating formulation in an amount of from about 5 to about 50 parts by weight per parts by weight of matrix vehicle. Advantageously, the composite coating formulation contains from about 5 to about 20 weight percent solid for ease of coating, although wider variations can be used if desired for particular situations.

Coating can be accomplished by a wide variety of techniques including flow coating, doctor blade coating, whirl coating, extrusion hopper coating, etc. The support material onto which the light-sensitive layer is applied is widely variable and includes such supports as cellulosic materials like cellulose acetate, cellulose acetate butyrate, etc., as well as polystyrenes, polycarbonates, polyvinyl compounds like polyvinylacetals, polyesters such as poly(ethylene terephthalate), poly-a-olefins like polyethylene, polypropylene and other poly-a-olefins conventionally having from two to 10 carbon atoms, and including metals like zinc and aluminum and paper including polyethylene and polypropylene coated papers.

Subsequent to coating and drying to form a composite photographic element of this invention, the resultant element can be imagewise exposed to actinic rays to prepare visible printout images. After exposure, heating like that previously described can be employed to intensity or stabilize the lightinduced photographic image. Stabilization, as noted above, is accomplished by exhausting unreacted halocarbon from the layer. lntensification results from the heat promoted action of an image intensifier like those described herein. Desirably, heating is within a range of from about 100 to about C., but wider variations in temperature can be used if desired.

The following examples are included for a further understanding of the invention.

EXAMPLE 1 A solution of 0.15 g. ofcompound l,from Table I, 0.15 g. of 6-diethylamino-4-methylcoumarin, 0.3 g. of carbon tetrabromide, and 0.03 g. of 2-methylbenzimidazole in 4 ml. of dichloroethane is added to ll ml. of a 10 percent solution of poly(vinyl butyral) dichloroethane and methanol (51]). The resulting solution is doctor blade coated on a paper support at a wet thickness of0.004 inch and allowed to dry. The resultant element is then exposed through a negative transparency in an Ozamatic Printer, manufactured by the Ozalid Corp., at a linear transport speed of 8 ft./min. to obtain a dark green, positive image on a white background. The Ozamatic printer uses a 1,200 watt high-pressure mercury arc lamp as an exposure source. Heat treatment for 10 seconds at 150 C. increases the image density, and stabilizes the print against further light reaction.

EXAMPLE 2 A solution of0.l5 g. of compound 3, from Table l, 0.15 g. of 6-diethylamino-4-methylcoumarin, 0.35 g. of carbon tetrabromide, and 0.03 g. of 2-methylbenzimidazole in 4 ml. of dichloroethane is added to 11 ml. of a poly(vinyl butyral) solution as in Example 1. The resulting solution is doctor blade coated on a paper support at a wet thickness of 0.004 inch and allowed to dry. The resultant element is then exposed and heated as in Example 1 to obtain an intensified, stable dark blue image on a light blue background.

EXAMPLE 3 To 4 ml. of a percent solution of a styrene-butylmethacrylate copolymer in dichloroethane is added a solution of 25 mg. of compound 1 from Table l, 25 mg. of carbon tetrabromide, 2.5 mg. of 2-methyl-benzimidazole, and 10 mg. of 6-diethylamino-4-methylcoumarin in 1 ml. dichloroethane. This solution is doctor blade coated on a paper support at a wet thickness of 0.004 inch and allowed to dry. The resultant element is exposed as in Example 1, but at a linear speed of 5 ft./min. Heat treatment at 150 C. for 10 seconds gives an intensified dark green, positive image on a white background.

EXAMPLE 4 A solution of 25 mg. of compound 7 from Table l, 5 mg. of Z-methylbenzimidazole, 25 mg. of carbon tetrabromide, and 10 mg. of 6-diethylamino-4-methyl-coumarin in 1 ml. dichloroethane is added to 4 ml. of a 10 percent solution of a styrene-butyl-methacrylate copolymer in dichloroethane. The solution is doctor blade coated on a paper support at a wet thickness of 0.004 inch and allowed to dry. The resultant element is exposed and heated as in Example 3 to give an orangebrown image on a light tan background.

EXAMPLE 5 A coating composition as in Example 4 but employing 25 mg. of compound 9 from Table l as the color-forming agent is doctor blade coated on a paper support at a wet thickness of 0.004 inch and allowed to dry. The resultant element is then exposed and heated as in Example 3 to give a dark tan, positive image on a pale yellow background.

EXAMPLE 6 A coating composition identical to that in Example 4, except employing 25 mg. of compound 3 from Table l as the color-forming agent, in lieu of compound 7, is coated at a wet thickness of 0.004 inch on a paper support and allowed to dry. The resultant element is then exposed and heated as in Example 3, to provide an intensified blue image on a white background.

EXAMPLE 7 A coating composition as in Example 3, except employing 25 mg. of compound 10 from Table I as the color-forming agent is doctor blade coated on a paper support at a wet thickness of 0.004 inch and allowed to dry. When exposed and heated as in Example 3, the resultant element gives an intensified, stable greenish-yellow image on a white background.

EXAMPLE 8 A solution of 25 mg. of compound 1 1 from Table l, 5 mg. of 2-methylbenzimidazole, 25 mg. of carbon tetrabromide, and 10 mg. of phenothiazine in 1 ml. dichloroethane is added to 4 ml. ofa l0 percent solution of poly(vinyl butyral) in a mixture of dichloroethane and methanol (5:1). This solution is doctor blade coated at a wet thickness of 0.004 inch on a paper support and allowed to dry. The resultant element is exposed and heated as in Example 3 to provide an intensified, stable yellow-orange image on a light yellow background.

The invention has been described in detail with particular reference to preferred embodiments thereof, but, it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

We claim:

1. A photographic element for the production of printout images and comprising a support having coated thereon a layer comprising a light-sensitive halocarbon compound that is decomposed on exposure to actinic rays and a 4H-pyran derivative that is a benzopyran or a naphthopyran having at least one aryl group substituted on the pyran ring, said pyran and said halocarbon compound being combined in a weight ratio of from 3:1 to |:5 respectivel 2. A photographic element as (described in claim I wherein the halocarbon compound is selected from the group consisting of halocarbon and polyhalocarbon compounds and wherein the 4H-pyran derivative has the formula:

wherein a. each of R and R represent a member selected from the group consisting of a hydrogen atom, an alkyl radical and an aryl radical and at least one of R and R is an aryl radical,

b. each of R and R when taken alone, represents a hydrogen atom, and

c. R and R when taken together, represent the atoms necessary to complete an aromatic ring system.

3. A photographic element as described in claim 2 wherein R represents a radical selected from the group consisting of a hydrogen atom, a methyl radical, an N,N-dimethylaminophenyl radical, and a p-methylphenylthio radical and R represents a phenyl radical.

4. A photographic element as described in claim 2 wherein R and R when taken together, represent a l,4-but-l,3- dienylene radical.

5. A photographic element as described in claim 3 wherein the methyl radical represented by R is selected from the group consisting of a l-ethoxycarbonyl-l-cyanomethyl radical, a lethoxycarbonyl-l-benzoylmethyl radical and a nitromethyl radical and the phenyl radical represented by R is selected from the group consisting of a phenyl radical, a p-ethoxyphenyl radical and a p-dimethylaminophenyl radical.

6. A photographic element for the production of printout images and comprising a support having coated thereon a layer comprising a halocarbon selected from the group consisting of carbon tetrabromide and dichloroethane and a 4H- pyran derivative as described in claim 3.

7. A photographic element for the production of printout images and comprising a support having coated thereon a layer comprising a carbon tetrabromide and a 4H-pyran derivative selected from the group consisting a. l-(p-N,N-dimethylaminophenyl) l H-3-(p-ethoxyphenb. 4-(p-N,N-dimethlaminophenyl)2-phenyl-4H- l -benzo[b] pyran c. lH-3-(p-N,N-dimethylaminophenyl)naphtho[2,l-b]- pyran d. l-(p-tolylthio)-lH-3-(p-ethoxyphenyl)naphtho-[2,l-b]

pyran e. 1-( l-ethoxycarbonyl-lcyanomethyl)- l H-3-(p-ethoxyphenyl)naphtho[2,l-b]pyran f. 4-( l-ethoxycarbonyll -cyanomethyl)-2-phenyl-4H- benzo[b]pyran g. l-( l-ethoxycarbonyl-l-ben2oylmethyl)-lH-3-(p-ethoxyphenyl)naphtho[2,l-b]pyran h. l-nitromethyl-lH-3-(p-(N,N-dimethylamino)phenyl)- naphtho[ 2, l -b lpyran, said pyran and said carbon tetrabromide being combined in a weight ratio of from 3:1 to 1:5 respectively.

8. A photographic image-forming process for the preparation of printout images on a photographic element as described in claim 1, which process comprises imagewise exposing said element to actinic rays, whereupon a printout image is produced in exposed ares.

9. A photographic image-forming process as described in claim 8 and additionally including heating said exposed element to intensify the printout image.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3121633 *Jul 25, 1962Feb 18, 1964Horizons IncProcess of making print-out images with cyanine dye bases and styryl dye bases
US3486899 *Dec 13, 1965Dec 30, 1969Minnesota Mining & MfgImagewise photochromic responsive element and process
US3532638 *Apr 28, 1967Oct 6, 1970Eastman Kodak CoPhototropic compositions
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3773508 *Nov 16, 1971Nov 20, 1973Fuji Photo Film Co LtdImagewise exposing and heating a photosensitive composition containing a spiropyran compound and an organic peroxide
US3844792 *Dec 7, 1972Oct 29, 1974American Cyanamid CoA photosensitive composition containing a photochromic benzoylchromone or dibenzofuran and a strong organic amine base
US3887808 *Jun 25, 1973Jun 3, 1975Agfa GevaertThermoimaging process utilizing a photochromic material containing a spiropyran, a polyhalogenated hydrocarbon, a thiol compound and a polyvinylcarbazole
US3907569 *Jan 31, 1973Sep 23, 1975Horizons IncUltraviolet holdback of nonsilver photosensitive systems by incorporating therein certain organic additives
US3973966 *May 8, 1974Aug 10, 1976Xerox CorporationPhotochromic composition containing a diphenyl dibenzochrom-3-ene
US3980480 *Jul 18, 1975Sep 14, 1976Urbain Leopold LaridonPhotographic recording and reproduction of information photochromic composition containing polyhalogenated hydrocarbon, spiropyran compound and heterocyclic mercapto compound and the use thereof
US4010033 *Mar 10, 1976Mar 1, 1977Agence Nationale De Valorisation De La Recherche (Anvar)Photosensitive layer and method of forming a photographic image therefrom
US4827149 *Oct 9, 1987May 2, 1989Sharp Kabushiki KaishaOperation halting circuit
Classifications
U.S. Classification430/332, 430/344, 430/962
International ClassificationG03C1/675, C07D311/92, C07D311/58, C07D311/60
Cooperative ClassificationC07D311/60, C07D311/58, Y10S430/163, G03C1/675, C07D311/92
European ClassificationC07D311/92, C07D311/60, C07D311/58, G03C1/675