US2071899A - Sensitized photographic film, plate, and emulsion - Google Patents

Description

Feb. 23, 1937. H. A. PIGGOTT ET AL T 2,071,899

SENSITIZED-PHOTOGRAPHIC FILM, FLATE, AND EMULSION Filed Dec. 4, 1935 -SENSlTIVlTY RANGE 0 PHOTOGRAPHIC EMULSION TREATEDYWITH DYESTUFF 0F EXAMPLE SENSITIVITY RANGE OF PHOTOGRAPHIC EMULSION TREATED WITH DYESTUFF 0F EXAMPLE INVENTQRS Henry Alfred P133011 Erna sTHaT'T-y Ru I ATTORNEY Patented Feb. 23, 1 937 I I I UNITED STATES PATENT OFFICE I SENSITIZED llAlggt iiglg zlzlilgfi FILM, rm'rs,

Henry Alired Piggott, Cheadle Hulme, and Ernest Harry Rodd, Brooklands, England, assignors to Imperial Chemical Industries Limited, a oorporation of Great Britain Application December 4, 1935, Serial No. 52,916 In Great Britain May 31, 1980 2 Claims. (01. 95-1) This invention relates to photographic sensitizthe metaand para-positions, R represents an in: compositions and to photographic preparaaliphatic hydrocarbon radical (not necessarily the tions, such as emulsions or plates or films coatedsame) Y represents the negative radical an with emulsions, comprising such compositions. acid (e. g., halogen, sulfate, oxalate, nitrate, chlo- This application is a continuation-in-part of rate, etc), and M represents a methenyl chain 5 our co-pendingapplication Serial No. 540,810 which may or may not be substituted by monovafiled in the United States May 28,1931, and in lent auxochromic substituents, for instance, by Great Britain May 31, 1930. aikyl, alkoxy or aryl groups or by halogen atoms It is known that a standard photographic emulsuch as chlorine, bromine or iodine. 1o sion is sensitive to light rays only within the It willbe recognized that this formula may also wave-length range of about 360 to 500 millimibe written:

crons, and'that by suitable treatment, e. g., by x z bathing ,a photographic plate in a dilute solution 01 a sensitizer, the emulsion becomes sensitive to light of other wave-lengths, but it is still a matter h I 15 or difliculty to increase or decrease the sensitivity B at will in any desired degree. 1

It is an object of this invention to produce new i z and improved sensitized photographic emulsions. X

A further object is to provide sensitizing compoj I/ N 20 sitions which will render photographic emulsions sensitive to light rays in the red and infra-red i; it,

region of the spectrum. It is a further object of this invention to provide photographicemulsions sensitive to red and infra-red light rays. It is also e posmon f the acid residue Y is t it 25 an object of this invention to provide plates and 1y known and it may be in equilibrium between films coated with such sensitized emulsions. I the two nitrogen atoms, other Ohlects will appear in the descrlphm and In carrying our invention into practical eiIect, claimh- I we treat a photographic emulsion with unsym- T ese o i t are achieved according to this i metrical polymethine dyestuffs as described so vention by h mp y of unsymmetrical above, e. g., by bathing a photographic plate in a p y m dyestuffs Such as can he Obtained by dilute aqueous solution oi'the dyestuii. The dyecondensing a heterocyclic nitrogen compound, t n maybe dd d to typical photographic emulcon flinl al rn l iv methylene g p sions, such as gelatino silver halide emulsions, in

5 with an intermediate compound obtainable by the a manner well known in the art. Preferably, a pr c described in our British Patent N solution of about 1 part of dyestufl in about 2000 344,409. In general, the sensitizing dyes employed parts of 50% aqueous alcohol is prepared. This in accordance with the pr n inv nii flnr stock solution is diluted for use with about 20 characterized by having the G n f mul parts of water. Approximately 100 cc. 0! the di- 0 luted solution are then taken for each full size 40 x photographic plate to be treated and the plate is 11 CM=C I a, immersed in the solution which is agitated gently and kept in contact with the plate for a period 0! 4 about five minutes. The plate is then washed 5 R Y with water and dried. It will be apparent to those wherein X represents a member oi the oxygen In the that the proportions or dyestufl and photographic emulsion may be varied in group oi elements or dialkylmethylene, Z repreorder to obtam the desired we 7 sents a member of the oxygen group of elements, The accompanying. drawing illustrates the Sam 5 dmkyl methylene. Vinylehe is diflereht sitivity curves of photographic emulsions treated 5 from X, B1 and R2 represent the same or diflerent t certain of t unsymmetrical dyegtuflg ortho-aromatic nuclei which may or may not be matter described. substituted by monovalent auxochromic substit- The invention will be rurther illustrated but is uents, e. g., 'by alkyl and alkoxy groups and/or not limited by the following examples, in which as halogen atoms such as chlorine and bromine in the parts are by weight.

flux for ten minutes in The reaction In and was filtered oil and formula .When a photograph solution of the dyestufl became sensitive to 11 the range 01' An intermediate compound condensing 9 ethiodide and 66 Twenty-four condensed w dolenine-methi teen minutes a solution 01' 50 pa tated dyestuii' purified It may be given the I Example I with 7 parts of 1:

this product. were condensed 3-trimethyl-2-methyleneindoline by boiling the two components under re- 2 parts 01' acetic anhyixture was then cooled,

ic plate was treated with a Esample II parts of acetic Example of our B parts of hydride to which 5 .-'I'he or the formula:

When photographic treated with the dyest the sensitivit millimiem y range is from was prepa ed by parts oi 2-methyl-benzothiaaoleparts oi diphenyl iormamidine anhydride. as described in ritish- Patent No. 344,409. this product were then 18 parts or 2:8:8-trimethyl-inodide in 160 parts of acetic anparts of sodium acetate had then diluted by or water and the precipiby lixiviation with ether. ormula:

plates and emulsions are uir as previously described about 360 to about dide and 66 parts of was purified by lixiviation with An alternate method of preparing the dyestuil' is to produce the intermediate compound from 2:3:3-trlmethyl-indolenine-methiodide and diphenyl i'ormamidine, as described in Example 1 of our British An intermediate product was prepared by boiling 58 parts of Z-methyl-benzoxazole-ethiodide 344,409. about 18 parts 2:3 3-trimethyl-indolenine-ethiodide under reflux in N/ or. 1 as,

When this dye is employed for sensitizing photographic plates and emulsions, as previously described, it extends the wave-length range and the plate becomes sensitive to wave-lengths 01' light within the range 01' 360 to about 600 milimicrons.

344.409, and then boil under reflux equi-molecular proportions oi said compound and 2-methylbenzoxazole-ethiodide in 160 parts of acetic anhydride and 5 parts or sodium acetate i'o'r fifteen minutes. The dyestui! may be separated as previously described.

Example IV An intermediate compound boiling 90 parts was prepared by oi 2-methyl-benzothiazole-ethio- Alternately, the dyestufl' may be prepared by making the intermediate product from 2-methyl benzoxazole-ethiodide, as described in Example 4 of our British Patent No. 344,409, and then condensing equi-molecular proportions of this intermediate product and 2-methyl-benzothiazoleethlodide in the presence of acetic anhydride and sodium acetate as previously described.

The dyestuii may be given the formula:

or the formula: n 0\ /s O-CH=CH-OH=C 0:134 \I I When photographic plates and emulsions are treated with the above identified dyestuff in the manner previously described, the range of sensi tivity to light is extended and the plate becomes chain. By

sensitive to a wave-length range from 360 to about 640 millimicrons.

It wil be apparent is applicable to the plates and emulsions dyestuffs of the type that the present invention treatment of photographic with other unsymmetrical described in the examples,

namely, those characterized by having dissimilar heterocyclic nuclei connected by a methenyl dissimilar nuclei" we mean nuclei which are substantially different, either in having dissimilar hetero atoms (as, for instance, an oxazole, thiazole or selenazole nucleus) connected through a methenyl chain to an indoline nucleus or a quinoline nucleus. Thus, in, Examples 11 and III, we have described dyestuffs in which a thiazole and an oxazole nucleus are connected through a methenyl chain to an indoline nucleus. By substituting chemically equivalent proportions of 2- methyl-benzoselenazole-ethiodide 'tor 2-methylbenzothiazole-ethiodide or 2-methyl-benzoxazoleethlodide in these examples, it will be apparent that we can obtain dyestuil's containing a selenazole nucleus connected through a methenyl chain with an indoline nucleus, said dyestuffs also being characterized by excellent sensitizing properties. Similarly, by neacting chemically equivalent proportions oi ethiodides of 2-methyl-benzoxazole, 2-methyl-benzothiazole or 2-methylbenzo'selenazole with the quinaldine ethlodide-diphenyl iormamidine condensation product of Example I in thepresence oi acetic anhydride and sodium acetate, we may prepare an oxazole, thiazole or selenazole nucleus connected through a methenyl chain to a quinoline nucleus.

It will also be apparent that we may employ dyes containing variouscombinatlons of oxazole,

selenazole and thiazole nuclei. Thus, our preterred dyes arethose in which the two heterocyclic nuclei are dissimilar in that they contain dissimilar atoms irom the'oxygen group of elements. Such a dye is described in Example IV in which a thiazole and an oxazole nucleus are connected by a methenyl chain. Instead of Z-methyl-benz oxazole-ethlodide in Example IV, we may employ the chemicallyequivalent proportions of 2- methyl-benzoselenazole-ethiodide to produce a dye in which through amethenyi chain to a thiazole nucleus; or, we may prepare the intermediate compound from a-methyl-benzoxazole-ethiodide and didyes containing a selenazcle nucleus is connected a dye containing an oxazole and a selenazole nucleus connected by a methenyl chain.

For simplicity in describing the invention, we

1 have'heretoiore referred specifically to the unsubstituted benzoxazoles, benzothiazoles andbenzoselenazoles, but it will be apparent to those skilled in the art that dyestufis containing auxochromic substituents, such as halogen atoms (e. g., chlorine or bromine), alkyl groups (e. g.,

methyl, ethyl, iscpropyl, butyl and higher homologues), and/or allroxy groups (e. g., methoxy, ethoxy, butyloxy, etc.) may be present in the aromatic nucleus in anyposition, or positions, but the ortho positions which are already 'fully substituted by the bonds from the heterocyclic ring. The method of preparing the dyestuffs from the substituted derivatives is the same as from the-unsubstituted derivatives, except that an intermediate is employed in which a substituent is already present. For instance, a 2- methyl-benzpselenazole ethlodide or' a 2-methylbenzothiazole-ethiodide in which the position mm to the carbon atom connectedto the sele-, nium, sulfur or oxygen atom is occupied by an atom or group such as chlorine, bromine, methyl,

ethyl, methoxy or ethoxy. Instead of the aromatic nucleus of theoxazcle, selenazole or thiazole being a benzene nucleus, it maybe a naphthalene nucleus, either substituted or unsubstituted.

Unslymmetrical dyes or the type described conheterocyclic nuclei connected 7 taining dissimilar by a pentawmethenyl chain may be prepared as described 'in our British Patent No. 355,693, by

reacting a beta-anilino-acrolein-anil and 2:3:3-

trimethyl-indoleni'ne allryl-icdide or Z-methyl- -benzothiazole-alkyi iodide or 2-"-methyl-.benzoselenazole -alkyl-iodide or 2-methy1-benzoxazolealkyl-iodide'in acetic anhydrlde to form an intermediate compound, intermediate compound with a 'z-methyl-benzothiazole-alkyl-iodlde, Z-methyl-benzoxazole-alkyl-iodideor Z-methyl-benzoselenazole-allwliodide in whic the member of the oxygen group of elements is dissimilar from that employed in the formation of the intermediate. This condensation may be c 'ried out in the presence of acetic anhydride and sodium acetate, as above described.

Unsymmetrical dyestuffs oi the type described containing substituents on the methenyl chain ploying alpha-substituted may be prepared by e beta-anilino-acroleinils invthe preparation of the intermediate bodies in accordance with British Patent No. 355,693, and then reacting the intermediate with the desired 2-methyl-benzothiazole ethiodide, 2-methyl-benzoxazole-ethiodide or 2-methyl-benzoselenazole-ethiodide, the choice of intermediate and/or reacting component being made so as to obtain a dye having, dissimilar heterocyclic nuclei. The dye is obtained by reacting the intermediate, for example, an intermediate prepared by heating approximately equimolecular proportions oi lino-acrolein anil in 200 parts of acetic anhydride to boiling 101' one hour as in Example 2 r British Patent No, 355,693, and then condensing the intermediate with an equi-molecular proportion and then condensing said alpha-chloro-beta-aniof Z-methyl-benzothiazole-ethiodide or 2 methy1- benzoxazole-ethiodide or 2-methyl-benzoselenazole-ethiodide in acetic anhydride containing potassium acetate, as in Example 4 of said patent. The resultant dyestufi will have a chlorine atom substituted on the methenyl chain. By employing the corresponding alpha-alkyland alpha- .alkoxy-substituted beta-anilino-acrolein-anils or other alpha-substituted derivatives, the corresponding substituents may be obtained on the methenyl chain. a

The course of reaction for the process of preparing the dyes as described in the examples -may be illustrated by the following equations:

(1) R/ Acid anhydride Diarylamidlne N NHCMH: R Y

CC H=CH N I l-Odin R Y O CH:

R1 +OaHsNHCOCHa Intermediate X (2) R( ;C CH=CH N-CuHg A Acid-bindin substance c. g, sodium acetate R1 0 wherein R, R1, R2, X, Y, Z and M have the fore going significance.

In the foregoing reactions, it will be recognized that equivalents may be employed, for example,

propionic enhydride for acetic anhydride or sodium propionate for sodium acetate. The for mation of the dye may also he effected in the presence of pyridine, alcohol or other solvents.

Preferred dyestufls of the inventionare such as may be represented by the general formula:

where A is a monovelent heterocyclic nitrogen residue of the type:

in which Ar and B have the some significance as before (though not necessarily representing identical groups), whilst Z stands for --O, -S or Se, or -CR: (R being alkyl) and is different from X.

It will be recognized that the results obtained with the 'difierent dyestuffs may vary. This is illustrated by the examples. The invention however, ofl'ers a wide selection of dyestufls of a particular type with which it is possible to obtain new and improved sensitized photographic plates, films and emulsions.

As many apparently widely difl'erent embodiments of this invention may be made without Acid anhydridc R:+e. g., acetic snhydrido-tdeparting from the spirit and Scope thereof, it is to be understood that we do not limit ourselves to the specific embodiments thereof except as delined in the appended claims.

We claim:

i. Photographic gelatino-silver halide emulsions containing an unsymmetrical polymethine ciyestufi having the following general formula:

in which X represents a member of the oxygen group of elements or dielkyl methylene, R1 represents' an aryl radical of the benzene series, R represents an alkyl radical, and Y represents the negative radical of an acid. 2. Photographic gelatino-silver halide emulsions containing an unsymmetrical polymethine dyestuif having the following general formula:

CH: CH

Ci ia I Y ALFRED PIGGOTT. nmms'r HARRY noon.

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