US3737316A

US3737316A - Two-equivalent sulfonamido couplers

Info

Publication number: US3737316A
Application number: US00176684A
Authority: US
Inventors: I Salminen; A Loria
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1971-08-31
Filing date: 1971-08-31
Publication date: 1973-06-05
Anticipated expiration: 1990-06-05

Abstract

4-SULFONAMIDO-SUBSTITUTED TWO-EQUIVALENT PHENOL- OR ANAPHTHOL-TYPE CYAN DYE-FORMING PHOTOGRAPHIC COUPLERS IN COLOR DEVELOPING COMPOSITIONS, IN COLOR PHOTOGRAPHIC SILVER HALIDE EMULSION COMPOSITIONS, ELEMENTS HAVING SUCH EMULSON COMPOSITIONS COATED THEREON, AND PROCESSES UTILIZING SUCH ELEMENTS.

Description

United States Patent 3,737,316 TWO-EQUIVALENT SULFONAMIDO COUPLERS Ilmari Fritiof Salminen and Anthony Loria, Rochester,

NAIRI glssignors to Eastman Kodak Company, Rochester, N0 Drawing. Filed Aug. 31, 1971, Ser. No. 176,684 Int. Cl. G03c 7/00 US. Cl. 96-566 28 Claims ABSTRACT OF THE DISCLOSURE 4-sulfonamido-substituted two-equivalent phenolor anaphthol-type cyan dye-forming photographic couplers in color developing compositions, in color photographic silver halide emulsion compositions; elements having such emulsion compositions coated thereon, and processes utilizing such elements.

This invention relates to 4-sulfonamido-substituted twoequivalent phenolor ot-naphthol-type cyan dye-forming couplers.

Color photographic images are obtained in the photographic art by coupling a silver image development byproduct (i.e., oxidized aromatic primary amino developing agents) with a color-forming coupler compound. The subtractive process of color formation is ordinarily employed and the resulting cyan, magenta or yellow image dyes are complementary to the primary colors. Coupler compounds employed to produce cyan photographic dyes, for instance, generally contain phenolic or u-naphtholic moieties.

Such phenolic or a-naphtholie couplers usually have various substituent groups on the ring which are capable of affecting various physical characteristics of the compound. Heavy substituent groups, for instance, may act as ballasting groups and tend to decrease solubility in aqueous alkaline processing compositions while increasing non-diffusible characteristics of a coupler in the hydrophilic layers of photo-elements during processing; the corresponding introduction of substituent groups such as halo or alkyl elsewhere on the same ring, however, may adversely or beneficially change the light stability of the image dye produced upon exposure and color development. The presence of an acylamido group on the ring may affect heat stability of some compounds, while the D value of a photographic image dye is sometimes increased by substitution of various other groups onto the No. 2 position on the aromatic nucleus. The abovedescribed changes are obviously not uniformly predictable or necessarily beneficial for all color photographic purposes.

In a color photographic system the color-forming coupler may be the unballasted or diifusible type which is conveniently introduced as part of the developing solution, or of the non-difiusible ballasted type which is initially incorporated into or contiguous with a light-sensitive photographic silver halide emulsion layer, both types being made available to react with oxidized color developing agent as a function of silver halide development to obtain a substantially non-ditlusible image dye.

Conventional color-forming coupler compounds of the phenolic or a-naphtholic configuration have an active CH= group at the No. 4 ring position which reacts with oxidized color developer, as indicated above, to produce an indoaniline dye. Dye-forming color photographic couplers of the above types are known and described as four-equivalent couplers, and are characterized in requiring the development of four light-exposed silver halide molecules in order to produce one molecule of dye.

Non-diifusible couplers of the four-equivalent type are ice exemplified, for instance, in US. Pats. 2,895,826, 2,474,- 293 and 2,908,573. Known diffusible (i.e., unballasted or lightly ballasted) couplers are conveniently exemplified in US. Pats. 2,113,329, 2,252,718 and 3,002,836.

Two-equivalent dye-forming couplers of the diffusible and, non-diffusible types are functionally characterized by requiring the development of only two exposed silver halide molecules during development to obtain one molecule of dye. Such couplers are generally derived from corresponding four-equivalent couplers of either difiusible or non-ditlusible types by replacing an available H atom in a coupling position (e.g., No. 4 ring position of a phenol or a-naphthol ring of a cyan dye-forming coupler) with a nonchromophoric coupling 011 group such as a fluorine atom, a chlorine atom, an acyloxy group, an aryloxy, an alkoxy, an arylthio, a cyclooxy group or a thiocyano group.

Both two-equivalent and four-equivalent type couplers of the water-soluble (i.e., Fischer type) and non-watersoluble types are utilized for present day color photographic purposes since the combination of characteristics required by modern technology may vary widely.

By way of example, it is important to obtain thinner, more durable photographic elements containing stable couplers which, in turn, produce lightand heat-stable photographic dyes having precise spectral absorption characteristics. The quality of the photographic image, for instance, depends to a large extent upon the relative solubility of certain coupler compounds in highand/or low-boiling organic solvents as described and utilized, for instance, in Julian, U.S. Pat. 2,949,360, in the light of earlier disclosures in Mannes, US. Pat. 2,304,939; Jelley et al., US. Pat. 2,322,827; Vittum, U.S. Pat. 2,801,170; and Fierke, US. Pat. 2,801,171. The use of minimal amounts of coupler solvent is desirable since the bulk, durability and optical opacity of the resulting photographic element is directly correlated to the amount of solvent employed and retained. This, in turn, affects image definition and resolution properties of the element.

Of equal importance is the need for non-difiusible couplers which may be homogeneously incorporated into silver halide emulsions in carefully controlled amounts without adversely affecting viscosity, adhesion, or the unity of any particular emulsion layer during modern high speed multilayer application onto a film backing. Undesired changes in viscosity of melted gelatin photographic emulsions may be caused by additives such as wetting agents, color components, type of gelatin, etc., and these changes directly alfect the coating characteristics of a photographic emulsion.

Including antihalation and gelatin interlayers, up to eight or more separate layers may be applied to a film base to obtain a modern color photographic element [ref. Kirk-Othmer, Vol. 5, pp. 812-845, (1964), Encyclopedia of Chemical Technology]. For this reason, any major coupler-induced changes in the adhesion or coating characteristics of a photographic layer are unacceptable. This general problem is recognized, for instance, on page 250 of the text by Zelikman and Levi, entitled Making and Coating Photographic Emulsions, The Focal Press, (1964), and also in British Pat. 1,193,321.

To achieve the above-indicated beneficial characteristics and to avoid corresponding undesirable features for modern color photographic purposes, it is necessary to ascertain which particular group of substituents favor a minimal number of undesirable characteristics While, at the same time, encourage a pro-conceived spectrum of favorable characteristics.

It is known, for instance, from Us. Pat. 2,362,598 of Vittum et al. that some couplers having sulfonamido substituents on the ring tend to form dyes having deficient heat and light stability. Improvement has been obtained in such cases, however, by attaching the nitrogen atom of the sulfonamido group to the No. 5 or 6 carbon (i.e., noncoupling positions) of the phenolic or naphtholic ring.

In addition, the known difliculty in obtaining non-diffusible type azine dyes from certain ballasted (non-diffusible) couplers is partly resolved in accordance with U.S. Pat. 2,569,906 of Starke by incorporating two ballasted alkyl or aryl sulfonamido groups onto a phenolic or aniline ring, the No. 4 position (coupling position) of the ring being specifically excluded from such substitution.

'From U.S. Pat. 2,53 6,010 of Schmidt et al., it is ascertained that phenolic-type couplers do not readily form azine dye images (i.e., etfect ring closure) unless the phenol ring is substituted in the meta position with an alkyl or aryl sulfonamido group.

It is not apparent, from the above teaching, whether certain sulfonamido substituent groups in the No. 4 coupling position will (1) remain functionally active in a beneficial way, or

(2) will beneficially aifect heat and light stability of the resulting dye obtained from the two-equivalent coupler compound as compared with the corresponding fourequivalent coupler compound.

It is an object of the present invention to obtain a new group of cyan dye-producing coupler compounds, corresponding color photographic emulsions, developer solutions and color photographic elements containing such coupler compounds.

It is a further object to obtain new cyan dye-producing two-equivalent coupler compounds which are easily obtained and which additionally produce dyes having improved light and heat stability as compared with corresponding known four-equivalent couplers.

It is a still further object to achieve the above objects without corresponding loss in image definition or resolution characteristics of a photographic element or material utilizing the new coupler, and without effecting undesirable viscosity changes in a photographic emulsion containing such couplers prior to or during application onto a film base or emulsion support.

The above objects are accomplished, for instance, by

vutilizing a 4-sulfonamido-substituted phenolor a 4-sulfonamido-substituted a-naphthol-two-equivalent cyan dyeforming photographic coupler in which the amido moiety of the 4-sulfonamido substituent is attached to the No. 4 carbon atom of the phenol or u-naphthol ring. Such compounds can be used in a photographic color processing .composition, as well as in phtographic silver halide emulsions. This unique class of coupler compounds is conveniently described in the general formula wherein R SO --NH- preferably represents a nonchromophoric radical attached onto the No. 4 carbon of the phenolicor a-naphtholic-ring of COUP; and

R is an alkyl or an aryl group, inclusive of straight or branched alkyls of 1-20 carbon atoms, exemplified by methyl, isopropyl, octadecyl and eicosyl, also an aryl group such as a phenyl or a naphthyl radical and inclusive of phenyl, naphthyl, and substituted phenyl or substituted "naphthyl'having at least one ring substituent such as an -alkyl or alkoxy having alkyl moieties of 1-20 carbon atoms, also a ring substituent such as a nitro, a carboxy,

a halo (e.g., chloro) or an alkyl-substituted carbonyl group such as propyl oarboxy.

Diifusible and non-diffusible couplers utilized within the scope of the present invention can also be conveniently represented by the general formulae:

in which (PHOL) and (NAOL) are defined respectively as a cyan dye-forming coupler moiety of the phenolicor the a-naphtholic-type, both having at least two ring substituent groups on the phenolic or a-naphtholic ring in addition to a hydroxyl radical; the

R S() --NH-group is defined as above and conveniently described as a wholly displaceable group upon reaction with oxidized color developer during color development,

the R moiety alone or in combination with any other part of the No. 4 substituent group being a non-chromophoric group which is further defined as being neither a photographic dye nor a dilfusible dye precursor of the type capable of a hypsochromic or bathochromic shift when subjected to a different environment such as a change in pH. Compounds utilizing preformed dyes or dye precursors of the type here excluded are disclosed, for instance, in a copending application by Fleckenstein, U.S. application 'Ser. No. 282,796 entitled Novel Sulfonamido Phenols, and in U.S. Pat. 2,756,142; the R group is also more precisely described as a No. 2 phenolic-ring substituent defined as a hydrogen atom, an alkyl group having up to 30 carbon atoms and preferably alkyl of 1-20 carbon atoms such as methyl, isopropyl, pentadecyl, and eicosyl, an alkoxy group having up to 30 carbon atoms, preferably alkoxy of 1-20 carbon atoms such as methoxy, isopropoxy, pentadecyloxy and eicosyloxy, or a substituent group of the formulae:

wherein is an alkyl group including an unsubstituted alkyl having up to 30 carbon atoms and preferably 120 carbon atoms, also including a substituted alkyl such as halo alkyl or polyhaloalkyl such as a fluoroalkyl or an aryloxy alkylene group wherein the alkylene moiety preferably contains up to about 15 carbon atoms and the aryloxy moiety, inclusive of a phenoxy or a naphthoxy group, can be additionally substituted by one or more of an alkyl, or alkoxy or a halo group, the alkyl or alkoxy moieties of such additional substituents can contain up to 30 carbon atoms and are exemplified by methyl, propyl, dodecyl, pentadecyl, eicosyl, methoxy and eicosyloxy; Ar is defined as an aryl group consisting of a phenyl or a naphthyl group having one or more of an alkyl, an alkoxy and a halo substituent group thereon, the alkyl moieties of said alkyl or alkoxy containing up to 30 carbon atoms and preferably 11-20 carbon atoms; R-; is a No. 2-naphtholic ring substituent defined as an alkyl group having up to 30 carbon atoms and preferably about 1-20 carbon atoms or a substituent group of the formulae:

(7) CONH-Ar wherein A, Ar and R are defined as above.

Corresponding dilfusible cyan dye-formingv couplers within the present invention are conveniently represented by Formulae 2 and 3 as described above, wherein R and R are defined as a hydrogen atom, an alkyl group having up to about 14 carbon atoms or an alkoxy group having up to about 14 carbon atoms such as methyl, dodecyl, methoxy, dodecyloxy, etc., the alkyl and alkoxy groups preferably having a lower alkyl moiety of 1-8 carbon atoms. R and R are also respectively defined in diffusible-type couplers as radicals of Formula 4 or 6 above,

wherein A is an alkyl group having up to about 14 carbon atoms and preferably lower alkyl of 1-8 carbons,

such groups being exemplified, for instance, by methyl,

isopropyl or dodecyl. Diifusible type couplers also preferably have either hydrogen, a halo radical, or lower alkyl group having up to about 8 carbon atoms, or lower alkoxy group having up to about 8 carbon atoms as substituents on the remaining available ring carbon atoms in the phenol or naphthol coupler moiety.

The non-diffusible couplers (i.e., those substantially Formula 9 is defined as in R and in Formula 8 additionally includes a radical of the formula YNH- in which Y is an acyl group including (1) An alkyl carbamyl group such as a substituted or unsubstituted alkanoic acid group having 1-20 carbon atoms including methylcarbonyl, a lauroyl group, an aryloxy alkyl carbonyl such as an alkylor dialkylphenoxyalkylcarbonyl and an arylcarbarnylalkylcarbonyl such non-migratory couplers remaining within the light-sensi- 10 as dimathylcarboxyphenylcafbamyloctylcarbonyl; tive silver halide emulsion) essentially constitute the resi- An arylcarbonyl group such as a p an y due of the compounds within the scope of Formulae 1-3 phenylhalosulfonylphenyl and corresponding p y (supra); in particular, those in which R and R are, recal'bollyl la r a hatarocyclic carbonyl having spectively, No. 2-phenolic or No. 2-ot-naph'tholic ring sub- 15 members 111 the T1118 nucleus and exemplified y a stituents defined as an alkyl group having at least about filmyl p; and 3 and 3 are Individually defined as a carbon atoms, preferably 15-30 carbons, or defined, hydrogen atom an alky1 Preferably low/Bf alkyl inclurespectively, as substituent groups of Formulae 4-5 or p of Carbon atoms such as a methyl or Octy1 6-7 (supra) in which A is an unsubstituted alkyl group constlfllallt-- taining at least about 15 carbon atoms and preferably 15- substlfllted .sulfonamldo P p lmfluded wlfhln the 30 carbon atoms, or a substituted alkyl such as an aryloxy p lnvsn'flon are convemently Obtalnad, for Instance, alkylene group wherein the alkylene moiety contains up by reacting a coTfesponding P11510101 p Lamina to about 15 carbon atoms, r fe bl 1 10 and the with the desired aryl sulfonyl halide. The reaction is demoxy moiety is inclusive of a phenoxy or a naphthoxy Onstfated y the equation group and may be additionally substituted by one or more (3()UP NH +X-SO R of an alkyl, an alkoxy, or a halo group, the alkyl or alkoxy moieties of the additional substituents preferably con- COUPFNH2 X s OOUP SO2 R' tainin about 1-20 carbon atoms; and in which Ar is defined i a phenyl or naphthyl group including those wherein X 15 a halo radical such as chloro, while ing one or more of an alkyl, an alkoxy and a halo sub- COUPNH stitnent thereon, the alkyl moieties of the alkyl or alkoxy containing at least about 15 carbon atoms. s a 4-am1no substituted four-equivalent cyan dye-produc- Two equivalent photographic coupler compounds of mg coupler of the above-defined type, and R is also deboth types Within the scope of the present invention also fa f l lr t l it r reaction mech'anism useful for obtainin 5 Include those represented by the formulae compounds such as Couplers XXIX-XL'I (infra) involves reacting a 2-nitro-4-aminophenol, with benzyl sulfonyl (8) 0H (9) chloride, reducing the 2-nitro group to obtain the amine and then further reacting the intermediate with a suitable R4 R1 alkyl-, aryl-, or heterocyclic-carbonyl chloride, followed 40 by nitration of the number 5 position, reduction of the R5 R5 nitro group, and then reaction of the resulting amine with l l benzoyl chloride to obtain the desired product. NHFSOFR NH SO2 R Suitable reaction mechanisms for obtaining the above COUPNH -(PHOL)-NH or (NAOL)NH re- Wherein 1 3, 7, and are defined as v 40 actant are well known in the art as evident, for instance, 2 is dafinsd as a hydrogen atom, a halo radical Such as from the Fieser text entitled Advanced Organic Chemischloro or fluoro, an alkyl group, including alkyl of 1-20 try, pages 620-627, 5th edition (1961), and from the recarbon atoms such as methyl, isopropyl, octyl, octadecyl, actions described in producing corresponding four-equiveicosyl, and chloromethyl and as an alkoxy group having alent and 4-chloro-substituted two-equivalent cyan dyean alkyl moiety of 1-20 carbon atoms, exemplified by forming couplers in US. Pats. 2,772,162 of Salminen et al. methoxy or eicosyloxy, hydrogen, lower alkyl and lower and US. Pat. 2,908,573 of Bush et al. alkoxy being preferred substituents; R is defined as a hy- The following couplers are listed to illustrate the drogen atom, a halo radical such as chloro or fluoro; an variety of compounds falling within the scope of the inalkyl group preferably lower alkyl of 1-8 carbons such as vention, it being noted that both ditfusible (i.e., intromethyl, isopropyl or octyl, and an alkoxy group, prefero duced during processing of exposed film) and nonably lower alkoxy of l-8 carbons such as octyloxy; R in diffusible-type couplers are included:

Coupler M.P. C.)

CH3- CH5 NHS O2 Coupler M.P. C.)

III OH 195-197 NHS 0:-

IV O H 196-202 0 H3) 2 C H- VI OH 129-134 0 Ha@ 0 H NH S O a C Ha VII .2 OH 192-200 VIII (DH 200-204 IX (|)H 186-200 NHS 03 X OH 133-135 Coupler M.P. (0.)

XI OH 156 NHSO2 XII (I311 129-131 NHSO2 XIII 311 202-204 finsm-QNO:

XIV OH 133-133 -CONHC4H -n IhHSOr-Q XV 0H 158-160 CONH(OHi)1O C5Hu t llTHSOr-QCHg XVI 11 CONH(CH2)4OC5H11(U 1 TH s mQ-o 0 on Additional couplers within the scope of the present invention include, for instance: XXXVI 2-[y-(2,4-ditert.-amylphenoxy)-butyrarnido]-4-phenyl- XVIL 2-N-dodecylcarbamyM-phenylsufonamido-naphthol.

XVIII 2-N-otilttalilelcylcarbarnyl-4-(pmethylphenylsulfonamido) nap o XIX 2-N-hexadecylcarbamyl-4-(p-octylphenylsulfonarnido) naphthol.

XX 2-N-octadecylcarbamyl-4-(octadecylsulfonarnido) naphthol.

XXI 2N-octadecylcarbarnyl-4-(methylsulfonamido)napl1thol.

XXII 2-(octadecylcarbonamido)-4-(phenylsu1fonarnido)phenol.

XXI Z-(hexadecylearbonamido)-4-(p-oarboxypheny1sulf0namido)phenol; and

XXIV 2-(dodecylcarbonamido)-4-(p-octy1phenylsulfonamido) phenol; also XXV 2-pentyl-G-Inethy1-4- (phenylsulfonamido) phenol.

XXVI 2-oetyloxy-4-(pheny1sulfonarnido) phenol.

XXVII. 2-octy1-5-methyl-4-(oetylsulfonamido) phenol; and

XXVlII 4-(octadeoylsulfonamido)phenol.

XXIX. 2-chloro-3methyl-4-phenylsulfonamido-6-[a-(3-n-pentadecylphenoxy)acetamido] phenol.

XXX Z-acetamidoA-phenylsulfonamido-fi-[a-(2,4-di-tert.-

amylphenoxy) acetamido] phenol.

XXXI 2-[ -(2,4-di-tert.-amylphenoxy)butyramido1-4-phenylsulfonamido-5-benzamidophenol.

XXXII 2,5-di-acetamido-4phenylsulfonamidophenol.

XXXIII- 2,5-di-lauroylamido-4-phenylsulionamidophenol.

XXXIV- 2-1agroylamido-4-phenylsulfonamidofi-iuroylarni dop eno XXXV. 2-['y-(2,4-di-tcrt.-amylphenoxy)-butyramido]-4-phenylsulfonamido-5-[5-(3,5-dicarbomethoxyphenylcarbamyl) valeramido] phenol. v

sulfonarnido-5-p-te1't.-amylbenzamidophenol.

XXXVIL 2,5-bis[a-(x-cl1loro-2,4-ditert.-amylphenoxy) acetamido1- 4-phenylsulf0namido-6-dichlorophenol.

XXXVIIL 4-phenylsulionamido-5-(3-chl0rosulfonylbenzamid0)-2- stearamjdophenol.

XXXIX. 2-(a-heptafluorobutyramido) -4-0ctadecylsulf0namido- 5-a (2,4-di-tert. amylphenoxy)-hexamidophenol.

XL 2-(a-heptafluorobutyramido)-4-(p-methylphenylsulf0narliiiidog-fi-a-(gl-di-tert. amylphenoxy) -hexamid0- p eno XLI 2-[N-(2,4 di-(t)-amylphenoxy)butylcarbamylli-(mnitrophenylsulfonamido) -naphthol.

The above compounds include both diffusible and nondiffusible two-equivalent type coupler compounds; couplers I-XIV and XXVXXVIII, for example, generally represent the diifusible type and XV-XXIV, the non-diffusible type.

Other types of 4-sulfonamido-substituted phenols and naphthol compounds are described in the concurrently filed and pending application of Fleckenstein and Figueras, US. Application Ser. No. 176,752, now abandoned and continued in part in Ser. No. 282,795 filed Aug. 22, 1972, entitled Diffusion Transfer Systems and Fleckenstein, US. Application Ser. N0. 176,751, now abandoned and continued in part in Ser. No. 282,796

filed Aug. 22, 1972, entitled Novel Sulfonamido Phenols, wherein the groups corresponding to R of Formula 1 (supra) are a pre-formed diffusible dye or a dye precursor such as a leuco dye or a shifted dye which shifts hypsochromically or bathochromically when exposed to a different environment such as a change in pH.

The ballasted non-difiusible type cyan couplers of the present invention are usefully incorporated into lightsensitive photographic silver halide emulsion layers and applied onto an emulsion support or film base in a singleor multi-layer color photographic material by known methods (example: the solvent and Fisher fat-tail methods) as described, for instance, in Mannes et al. in U.S. 2,304,939-40 and Jelley et al. in U.S. Pat. 2,322,027, in which high-boiling organic solvents are used to dissolve the coupler. Further useful procedures are described, for instance, in Vittum et a1. U.S. Pat. 2,801,170; Fierke ct al. US. Pat. 2,801,171 (July 1957); and Julian U.S. Pat. 2,479,360 (August 1960), whereby low-boiling or water-soluble organic solvents are used with or in place of a high-boiling solvent. In the case of multi-layer photographic materials or elements, the non-ditfusible coupler compounds are generally incorporated into the redsensitive silver halide emulsion layer and preferably utilize minimal amounts of high-boiling solvents.

Generally speaking, a useful coupler concentration will vary from about 25-200 mg./ft. of coated material, a range of 30-50 mg./ft. being generally satisfactory for use in photographic paper, with overlapping and higher concentrations found useful in color photographic films.

A variety of color coupler-containing photographic materials and elements are obtainable utilizing the above family of cyan dye-producing couplers. Generally speaking, however, such photographic materials and elements will comprise the following main components:

(A) A support layer such as cellulose nitrate film, cellulose acetate film, polyvinylacetal film, polystyrene film, poly( ethylene terephthalate) film, polyethylene film, polypropylene film and related films of resinous materials as well as paper, polyethylene coated paper, glass, and others. The terms include paper or other flexible fibrous material which can be partially acetylated or coated with baryta or some other hydrophobic film or surface which repels and does not absorb or adsorb Water. A support layer having a hydrophobic surface can also include hydrophobic resin layers Which have been subject to a corona treatment as described, for instance, in British Pats. 971,058, 1,060,526 and U.S. Pats. 2,864,755 and 2,864,756 to improve adhesion of hydrophilic colloid layers coated over them. Such resin layers or films may be either self-supporting or may be coated over another support layer. Specific supports ha'ving useful hydrophobic surfaces include polyethylene terephthalate films electronbombarded to have a contact angle less than 45 (U.S. Pat. 3,220,842), a corona-treated surface comprising a chromium halide (U.S. Pat. 3,117,865), or corona-treated hardened gelatin coated papers (Belgian Pat. 671,661), etc. The support layer may also contain various functional additives such as titanium dioxide, zinc oxide, and silica as suggested in U.S. Pats. 2,992,101 and 2,701,245, and anti-static agents as described, for instance, in U.S. Pat. 3,253,922;

(B) An antihalation layer such as a dye-containing gelatin, starch, etc., as described, for instance, in Glafkides Photographic Chemistry, volume 1, pages 470-471, Arrowsmith Ltd. 1958;

(C) One or more, preferably three light-sensitive and diflerently-sensitized color coupler-containing silver halide emulsion layers coated onto the support, optionally with one or more gelatin spacer layers between. The support is conveniently coated in succession with a red-sensitive layer containing one or more of the above-defined class of cyan-dye-producing coupler, a green-sensitive layer and a blue-sensitive layer, either with or without a Carey- Let filter layer between the blueand green-sensitive 12 layers. The three differently color-sensitized layers can also be arranged in any other order over one another that is desirable, with the exception that a Carey- Lea filter layer cannot be placed over a blue-sensitive layer.

The light-sensitive silver halide emulsions can include coarse, regular, or fine grain silver halide crystals or mixtures thereof such as silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chloroiodide, silver chlorobromoiodide and mixtures thereof; such emulsions are described, for instance, in The Photographic Journal, volume LXXIX, May 1939, pages 330-338; Journal of Photographic Science, volume 12, No. 5, Sept./ Oct. 1964, pages 242-251, and also in U.S. Pats. 2,184,013, 2,456,953, 2,541,472, 2,563,785, 3,367,778 and 3,501,307. In addition to the cyan-dye-forming couplers of the present invention such emulsions used in greenand blue-sensitive layers can include twoand four-equivalent magentaand yellow-dye-producing couplers of the type described, for instance, in U.S. Pats. 2,453,661, 2,449,966, 2,521,908, 2,908,573, 3,311,476, 3,476,563, 3,152,896 and 3,062,653.

Ballasted two-equivalent couplers of the present invention are usefully incorporated within gelatin, colloidal albumin, cellulose derivatives or synthetic resins, as described in U.S. Pat. 2,286,215 or 2,327,808, water-soluble ethanol amine cellulose acetates as described in U.S. Pat. 2,322,085, also suitable polyacrylamides having a combined acrylamide content of 30-60% and a specific Viscosity of .25-1.5 on an imidized polycerylamide of similar acrylamide content and viscosity such as described in U.S. Pat. 2,541,474, in Zeil as described in U.S. Pat.

2,563,791, into a vinyl alcohol polymer containing urethane carboxylic acid groups of the type described in U.S. Pat. 2,768,154, or one containing cyano-acetyl groups, exemplified by vinyl alcohol-vinyl cyanoacetate copolymers as described in U.S. Pat. 2,808,331, a polymeric material from a protein polymerisate or a saturated acylated protein with a monomer having a vinyl group described in U.S. Pat. 2,852,382.

(D) One or more gelatin spacer layers between the light-sensitive emulsion layers or the emulsion layers and Carey-Lea filter layer as above described; and

(E) A protective water-permeable overcoat layer, such as gelatin, poly-N-vinyl lactam, gum arabic, hydrophilic copolymer of N-acrylamindoalkyl betain (ref. U.S. Pat. 2,833,650), cellulose ethers and esters, alkali soluble polyvinyl phthalate (ref. U.S. Pat. 2,798,004); also watersoluble polymers having varying degrees of solubility, such as polyvinyl alcohol (optimally with surfactant), polyvinyl pyrrolidone polyalkylene oxides, polyvinyl alcohol and its derivatives such as partial esters, ethers and acetals exemplified by hydrolyzed polyvinylacetate, polyvinyl acetaldehyde acetal, polyvinyl butyraldehyde acetal, polyvinyl sodium o-sulfobenzaldehyde acetal, polyvinyl disodium 2,4 disulfobenzaldehyde acetal; and water-soluble copolymers and interpolymers exemplified by copoly (methyl vinyl ether/maleic anhydride), copoly(acrylic acid/methacrylic acid ethyl ester-maleic anhydride) and copoly (maleic anhydride/ acrylic acid/vinyl acetate). The overcoat may conveniently contain aldehyde scavenger such as described, for instance, in U.S. Pats. 3,236,- 652, 3,287,135, 3,220,839, 2,403,927, and British Pat. 623,448, and other ingredients such as buffering agents (e.g., an acidic or basic material), and ultra-violet light absorbers such as 2,2'-di-hydroxy-4,4' dimethoxybenzophenone, 4,4 dimethoxybenzophenone, 4,4 diazidostilbene 2,2 disulfonic acid sodium salt, and sodium- (a-phenylhydrazone).

In addition, photographic materials and elements utilizing the present cyan-dye-forming couplers can usefully contain brighteners such as stilbenes, triazines, oxazoles and coumarins as described, for instance, in German Pats. 972,067, 115,024, and in U.S. Pat. 2,933,390; they may also contain spectral sensitizing dyes to impart additional sensitivity to light-sensitive silver halide emulsion layers.

G./l. Development accelerator -50 Color developing agent 2-100 Alkali metal bromide 0-100 Antifoggant 01.0 Alkali metal iodide 0-1.0 Alkali metal chloride 0-25 Soluble ditfusible competing coupler 0-500 Buffer 0-100 Silver halide solvent 0-50 Antioxidant 0-50 pH range, 8.0 to 14.0.

wherein the pH is conveniently adjusted with an alkali metal or ammonium hydroxide.

Development accelerators for use in the above-type formulation include, for instance:

benzyl alcohol p-cresol phenyl ethyl alcohol p-n-amyl phenol n-octyl alcohol and p-sec.-butyl phenol The color developing agents found useful in the present invention are customarily of the p-phenylene-diamine type and include:

p-amino-N,N-diethylaniline HCl 4-amino-3-methyl-N,N-diethylaniline HCl 4-amino-N-ethyl-N-fl-hydroxyethylaniline H 80 4-amino-N-butyl-N-w-sulfobutylaniline 4-amino-3-methyl-N-ethyl-N-p-hydroxyethylaniline H 80 4-amino-3-methyl-N-ethyl-N-i3-(methane sulfonamido )ethylaniline 3/2 H SO --H O 4-amino-3-B- methanesulfonamido) ethyl-N,N-diethylaniline HCl 4-amino-3-methoxy-N-ethyl-N-B-hydroxyethylaniline 2HCl, and N,N-diethyl-3-(2-hydroxyethyl)-p-phenylenediamine 2HCl, while useful antifoggant components are demonstrated, for instance, by

benzotriazole 5-nitrobenzimidazol nitrate S-nitroindazole I-phenyI-S-mercaptotetrazole S-methylbenzotriazole, and N-methylbenzothiazolium-p-toluene sulfonate, etc.

Useful buffers in color developing formulations can include alkali metal salts such as:

an alkali metal salt of boric acid, etc., or organic buffers, such as described in Bard et al., U.S. Pat. 3,305,364, etc.

Useful silver halide solvent for the above purpose includes:

2 2 NaCNS NH OH ethylenediamine 14 dithiooctanediol thiourea isopropylamine, and n-butylamine, etc.; and useful antioxidants include:

hydroxylamine sulfate diethylhydroxylamine sodium sulfite dextrose p-hydroxyphenyl glycine ascorbic acid oxytetronic acids and dihydroxyacetone; while suitable optional soluble competing couplers are exemplified, for instance, by

a-pivaloylacet-4-sulfoanilide u-pivaloylacet-2-sulfoanilide a-pivaloylacet-2,4-dicarboxyanilide 3-arnino-l-(4-sulfophenyl)-5-pyrazol0ne 3- (4-sulfoanilino l- (chlorophenyl) -5-pyrazolone 3-amino-1-(4-sulf0phenyl) -4-thiocyano-S-pyrazolone 1-amino-8-naphthol-3,6-disulfonic acid 2-amino-5-naphthol-7-sulfonic acid 1,8-dihydroxynaphthalene-3,6-disulfonic acid 2,6-dihydroxyisonicotinic acid 3,5-dihydroxybenzoic acid methyl 2,6-dihydroxyisonicotinate u- (4-sulfobenzoyl) -a-chloroacetanilide ot-(4-carboxybenzoyl)- x-chloro-wcarboxyacetanilide, and

a-(4-hydroxybenzoyl)wt-chloro-w-sulfoacetanilide additional competing couplers of this type are further described in U.S. Patent Application S.N. 52,721, now U.S.

Patent 3,647,452, of Hendess et al. filed on July 6, 1970. This invention is further described, although not limited, by the following examples:

EXAMPLE ICOUPLER I A mixture of 17.37 gm. (.1 mol) 4-amino-2,6-dimethylphenol hydrochloride and ml. pyridine are cooled in an ice bath and 19.43 gm. (.11 mol) of benzenesulfonyl chloride added, with stirring, under a nitrogen atmosphere for 2.5 hours. The mixture was thereafter poured onto ice and concentrated HCl and the resulting gummy product, separated and recrystallized from an ethanol- Water mixture and identified as 2,6-dimethyl-4-benzene sulfonamido phenol (M.P. 154l57 C.).

EXAMPLE IICOUPLER VI A mixture of .1 mol 4-am-ino-2,6-dimethyl phenol hydrochloride and 150 ml. pyridine are cooled and slowly reacted with about .11 mol of methylsulfonyl chloride, with stirring, under a nitrogen atmosphere as in Example 1, and the resulting product recovered and recrystallized to obtain a crystalline material identified as 2,6-dimethy1- 4-methylsulfonamido phenol (M.P. 129-134 C.).

EXAMPLE IIICOUPLER XV EXAMPLE -IVCOUPLER XXIX A mixture of .1 mole of 3-n-pentadecyl phenol, .11 mole of potassium hydroxide pellets, and 150 ml. of xylene is stirred and boiled until 75 ml. of xylene is collected. To the remainder, is added .1 mole of sodium chloroacetate and refluxed for three hours; the product is then cooled and audified and the crystallized intermediate recovered and reacted with excess thionyl chloride at 50'56 C. for four hours and the excess thionyl chloride removed under vacuum; .01 mole of the a-(3pentadec'ylphenoxy) acetyl is then reacted in the presence of: .03 mole anhydrous sodium acetate in 90% acetic acid with .01 mole of 2 chloro-3-methyl-4-arnino-6-nitrophenol hydrochloride obtained from 2-chloro-3-methylphenol by coupling with a diazonium salt, followed by reduction to obtain the pamino derivative, and then nitration to the o-position and reduction; the reaction product of 2-chloro-3-rnethyl-4- amino-6-nitrophenol and the above-described octyl chloride recovered and identified as Coupler XXIX. 1

EXAMPLE V-COUPLER XXXVIII To a solution of .1 mole of S-amino Z-stearamido phenol in 60 volumes dioxane is added .11 mole 3-chlorosulfonylbenzoyl chloride in 15 volumes of dioxane at C.; an aqueous slurry'of the product is then filtered,

crystallized from ethyl acetate, then nitrated and reduced to the 4amine, and thereafter reacted with .11 mole of benzylsulfonyl chloride to obtain the corresponding 4- phenyl sulfonylamido derivative identified as Coupler X)Q(VIII.

EXAMPLE VICOUPLER XXXII By utilizing .1 mole of 5-amino-2-acetamidophenol and .11 mole of acetyl chloride in place of the S-arnino-Z- stearamidophenol and 3-chlorosulfonyl'benzoyl chloride in the process of Example V, there is obtained a compound identified as Coupler XXXII.

EXAMPLE VII-COUPLER XXXIII By utilizing .1 mole of 5-arnino-Z-lauroylamidophenol in place of S-amino-Z-stearamidophenol and .11 mole of laurylsulfonylchloride in place of benzylsulfonyl chloride in the process of Example V, there is obtained a compound identified as Coupler XXXIII.

EXAMPLE VIII-COUPLER XXXIV By utilizing .1 mole of 5-aminoQ-lauroylamidophenol in place of S-arnino-2-stearamidophenol and .11 mole of furoyl chloride in place of 'benzoylsulfonyl chloride in the process of Example V, there is obtained a compoun identified as Coupler XXXIV.

EXAMPLE IX Three coupler-free single-layer teststrips are prepared by coating cellulose acetate support with light-sensitive gelatin-silver bromoiodide emulsion; the teststrips are exposed to a light source through a 03.0 1) step wedge, and developed to obtain a silver image which is then fixed .and treated with K Fe(CN) and KBr in the usual man- (A) Three film test strips are prepared by coating cellulose acetate film base with a single layer of lightsensitive bromoiodide test emulsion, containing gelatin (450 mg./ft. silver (126 mg./ft. and a'coupler of the formula rug/ft?) dissolved in dibutyl phthalate 40 mg/ ft?) and dispersed into the gelatin. The coated strips are then exposed to alight source through a step wedge and color developed in theusual manner using the following color developer composition:

H O -ml 800 Sodium hexametaphosp ate- ,g 0.5 Na SO 2.0 4 arnino 3 methyl N,N diethyl aniline hydrochloride g 2.0 Nazcoa, H2O .I.. Q g 50% NaBr solution ml 3.4

The developed strips are then tested for light fading, heat fading, print out and yellowing inthe manner described and the results reported in Table I (infra).

a (B) Three film test stripsare prepared and tested asin A (sup a but with thev same amount of 1-hydroxy-4- chloro 2 N[w(2,4di-tert.-amylphenoxy)butyl]naphthamide (i.e., .the two-equivalent4-chloro analog) as the coupler, and the test results reported in Table I.

(C) Three film test strips are prepared and tested asin A (supra) but with Coupler XV having the formula Coupler XV 7 ficosmwmnoQ-cmm l CEHHU) l NHSO2-CH3 (D) Three test strips are prepared and tested as in A, utilizing as coupler 2,S-di-lauroylamidophenol obtained MP 158160C:

-fromthe corresponding 5-amino-2-lauroylamidophenol and lauroyl chloride in accordance with the process described in Example V, and the test results reported in Table I.

(E) Three test strips are prepared and tested as in A, utilizing Coupler XXXIII (the two-equivalent 4-phenyl sulfonamido-- derivative) and the test results reported in Table I. e

(F) Three test strips are prepared and tested as in A, utilizing as a coupler, a compound of the forrnn CSHUQ) obtained in accordance with the process described in Example V, and the test results reported in Table I.

(G) Three test strips are prepared and tested as in A, utilizing as a coupler, a compound of the formula causes unwanted stain under the influence of light is determined by exposing processed coatings to SANS, as above described, and recording the resulting increase in density to blue light (420 mg) in a D min area of the coating. This increase is termed Printout (PO) and is recorded in terms of percent density increase.

Heat fading tests The extent to which the image dyes fade under the influence of heat and humidity is determined by subjecting coatings to a temperature of 60 C. at a relative humidity of 70% for 1 week. The resulting decrease in image dye density is termed Heat Fade (H.F.) and is measured in terms of decrease in dye density in density units. The effect of heat on unreacted coupler is determined by subjecting coatings to the above heat and humidity conditions, and determining the increase in density (i.e., yellowing) in a D min area (420 lTl/L) of the coating, and recording this in terms of percent density increase.

1 Contains a coupler of the invention.

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

We claim:

1. A photographic silver halide emulsion containing a phenol or a-naphthol photographic color coupler having substituted in the No. 4 position of the phenolic and a-naphtholic ring a sulfonamido group wherein the amido moiety of the sulfonamido group is attached at said No. 4 position.

2. A photographic silver halide emulsion containing a cyan-dye-forming color coupler compound of the formula wherein COUP is the residue of a cyan dye-forming coupler moiety of the phenolic or u-naphtholic type; R SO NH represents a non-chromophoric radical attached onto the No. 4 carbon of the phenol or u-naphthol ring of COUP; and R is an alkyl or an aryl group.

3. A photographic silver halide emulsion or emulsion layer containing at least one cyan dye-forming color coupler compound of the formulae R' (NAOL)NHSO R wherein (PHOL) and (NAOL) are respectively defined as a cyan-dye-forming coupler moiety of the phenolic or the u-naphtholic type, the

R SO NH group being a No. 4 phenolicor No. 4-a-naphtholic ring substituent, the R moiety alone or in combination with any other part of the No. 4 ring substituent group being a non-chromophoric group and defined as an alkyl or an aryl group;

R is a No. 2 phenolic ring-substituent defined as a hydrogen atom, an alkyl group having up to 30 carbon atoms,

NHCO--A or -NHCOAr wherein A is an unsubstituted alkyl group having up to 30 carbon atoms, a halo alkyl, or an aryloxy alkylene group; Ar is defined as an aryl group having one or more of an alkyl, an alkoxy, or a halo substituent group thereon, the alkyl moiety of said alkyl or alkoxy groups containing at least 15 carbon atoms; and

R7 is a No. 2 a-naphtholic ring substituent defined as an alkyl group having up to 30 carbon atoms,

4. A photographic silver halide emulsion or emulsion layer containing at least one cyan-dye-forming coupler compound of the formulae wherein (PHOL) and (NAOL) are respectively de fined as the residue of a four-equivalent cyan-dyeforming coupler moiety of the phenolic or a-naphtholic type having at least two substituent groups in phenolic or a-naphtholic ring in addition to a hydroxy radical, th'e R SO -NH-group being a No. 4 phenolicor No. 4 u-naphtholic-ring substituent, the R moiety alone or in combination with any other part of the No. 4 ring substituent being a nonchromophoric group and defined as a straight or branched chain alkyl having 1-20 carbon atoms, a phenyl group, or a naphthyl group;

R is a No. 2 phenolic ring substituent defined as an alkyl group having at least 15 carbon atoms in which A is an unsubstituted alkyl group containing at least 15 carbon atoms, a halo alkyl, or an aryloxy alkylene group wherein the alkylene moiety contains up to 15 carbon atoms;

Ar is a phenyl or a naphthyl group; and

R is a No. 2 u-naphtholic ring substituent defined as an alkyl group having at least 15 carbon atoms,

5. A photographic silver halide emulsion or emulsion layer of claim 3 wherein -(PHOL) and (NA-OL)-, respectively, have the formulae in which R is defined as a hydrogen atom, a halo radical, an alkyl group having 120 carbon atoms, or an alkoxy group having an alkyl moiety of 1-20 carbon atoms;

R, is defined as a hydrogen atom, a halo radical, an

alkyl group, or an alkoxy group;

R in Formula 9 is defined as R, and in Formula 8 additionally includes a radical of the formula in which Y is an alkanoic acid group, an arylcarbonyl grou or a heterocyclic carbonyl having 5-6 members in the ring nucleus; and R and R are individually defined as a hydrogen atom or an alkyl group.

6. A photographic silver halide emulsion of claim 4 wherein R is a hydrogen, a lower alkyl, a lower alkoxy, or a halo group;

R is a hydrogen atom, a halo group, a lower alkyl group, or a lower alkoxy group;

R is defined as R; and additionally includes a radical of the formula YNH- in which Y is a fatty acid acyl group, an aryl carbonyl group, or a heterocyclic carbon carbonyl having 5-6 members in the ring nucleus; and

R and R are individually defined as a hydrogen atom or lower alkyl group.

7. A photographic silver halide emulsion of claim 4 wherein -(NAOL)- is a four-equivalent cyan dyeforming coupler moiety of the a-naphtholic type;

R is phenyl, lower alkyl phenyl, or carboxyphenyl; and

R is a radical of the formula CONHA in which A is a 2,4-di- (t)-amylphenoxybutylene group.

8. A photographic silver halide emulsion containing a cyan dye-forming coupler compound of the formula corrmomnoQ-cmflo Ca n) nnsmQom 9. A photographic silver halide emulsion containing a cyan dye-forming coupler compound of the formula NHSOr-QCO on 10. A photographic silver halide emulsion containing a cyan dye-forming coupler compound of the formula 11. A photographic silver halide emulsion containing a cyan dye-forming coupler compound of the formula (W n s 12. A photographic silver halide emulsion containing a cyan dye-forming coupler compound of the formula 13. A color photographic element comprising a support and at least one photographic silver halide emulsion containing a cyan dye-forming coupler compound of the formula COUP--NH-SO -R wherein COUP is the residue of a ballasted non-diffusible cyan dye-forming coupler moiety of the phenolic 0r a-naphtholic type;

R SO -NH-- represents a non-chromophoric radical attached onto the No. 4 carbon of the phenolic or u-naphtholic ring of COUP; and

R is defined as an alkyl or an aryl group.

14. A color photographic element comprising a support and at least one photographic silver halide emulsion containing a cyan dye-forming coupler compound of the formulae in which --(PHOL)- and (NAOL)-- are respectively defined as the residue of a cyan dye-forming coupler moiety of the phenolicor a-naphtholic-type having at least two substituent groups on the phenolic or a-naphtholic ring in addition to a hydroxyl radical;

R SO NH- is a No. 4-phenolicor a No. 4-naphtholic-ring substituent, the R moiety alone or in combination with any other part of the No. 4 substituent group being a non-chromophoric group and defined as an alkyl or an aryl group;

R is a No. 2 phenolic ring substituent and defined as an alkyl group having at least 15 carbon atoms,

in which A is an unsubstituted alkyl group containing at least 15 carbon atoms or an aryloxy alkylene group wherein the alkylene moiety contains up to 15 carbon atoms; and

Ar is a phenyl or a naphthyl group;

15. A color photographic element comprising a support and an emulsion layer as defined in claim 7.

16. A color photographic element comprising a support and an emulsion layer as defined in claim 8.

17. A color photographic element comprising a support and an emulsion layer as defined in claim 9.

18. A color photographic element comprising a support and an emulsion layer as defined in claim 12.

19. An aqueous alkaline color photographic developing composition comprising an aromatic primary amino color developing agent and a phenol or a-naphthol photographic diffusible color coupler having substituted in the No. 4 position of the phenolic and a-naphtholic ring a sulfonamido group wherein the amide moiety of said sulfonamido group is attached at said No. 4 position.

20. An aqueous alkaline color photographic developer composition comprising a p-phenylene-diamine color developing agent and a diffusible cyan dye-forming coupler compound of the formula in which (COUP) is a cyan dye-forming coupler moiety of the phenolic or u-naphtholic type;

R SONH is a non-chromophoric No. 4 phenolicor No. 4-naphtholic-ring substituent wherein R is an alkylor an aryl group;

R is a hydrogen atom, an alkyl group having up to 14 carbon atoms, an alkoxy group having up to 14 carbon atoms,

wherein A is an alkyl group having up to 14 carbon atoms.

21. An aqueous alkaline color photographic developer composition comprising a p-phenylene-diamine color developing agent and a difiusible cyan dye-forming coupler compound of the formula wherein R is a phenylsulfonamido, a naphthyl sulfonamido, or an alkyl sulfonamido group having 1-20 carbon atoms;

R, is a hydrogen atom, a halo radical, a lower alkyl group, or a lower alkoxy group;

R and R are each a hydrogen atom, an alkyl group having up to 14 carbon atoms, an alkoxy group having up to 14 carbon atoms,

wherein A is an alkyl group having up to 14 carbon atoms; R are each a hydrogen atom, a halo radical, a lower alkyl group, or a lower alkoxy group. 22. A color photographic developer composition comprising a p-phenylene-diamine color developing agent and a ditfusible cyan dye-forming phenolic or u-naphtholic type coupler selected from the group consisting of 23. A color photographic developer composition of claim 22 wherein the cyan dye-forming coupler is 24. A color photographic developer composition of claim 22 wherein the cyan dye-forming coupler is NHSO 25. A color photographic developer composition of claim 22 wherein the cyan dye-forming coupler is NHS 0 26. A color photographic developer composition of claim 22 wherein the cyan dye-forming coupler is OH I NHS 02- 27. A color photographic developer composition of claim 22 wherein the cyan dye-forming coupler is NHSm-QNO,

28. The process for color developing an imagewise exposed photographic element comprising a support having coated thereon a photographic silver halide emulsion containing a phenol or a-naphthol photographic color coupler having substituted in the No. 4 position of the phenolic and a-naphtholic ring a sulfonamido group wherein the amido moiety of the sulfonamido group is attached to said No. 4 position, which process comprises develop ing said photographic element with an aqueous alkaline solution containing an aromatic primary amino color developing agent, and resulting oxidized color developing agent reacting in areas of silver halide development with said No. 4 position of said phenolic or a-naphtholic ring to form a dye with said ring.

References Cited UNITED STATES PATENTS 2,356,475 8/1944 Schinzel 96-566 2,362,598 11/1944 Vittum et al. 9656.6

NORMAN G. TORCHIN, Primary Examiner R. L. SCHILLING, Assistant Examiner US. Cl. X.R. 96100