Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/42—Structural details
  • G03C8/44—Integral units, i.e. the image-forming section not being separated from the image-receiving section
  • G03C8/48—Integral units, i.e. the image-forming section not being separated from the image-receiving section characterised by substances used for masking the image-forming section
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B11/00—Diaryl- or thriarylmethane dyes
  • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B11/00—Diaryl- or thriarylmethane dyes
  • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
  • C09B11/06—Hydroxy derivatives of triarylmethanes in which at least one OH group is bound to an aryl nucleus and their ethers or esters
  • C09B11/08—Phthaleins; Phenolphthaleins; Fluorescein
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B11/00—Diaryl- or thriarylmethane dyes
  • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
  • C09B11/10—Amino derivatives of triarylmethanes
  • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
  • C09B11/245—Phthaleins having both OH and amino substituent(s) on aryl ring
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B11/00—Diaryl- or thriarylmethane dyes
  • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
  • C09B11/26—Triarylmethane dyes in which at least one of the aromatic nuclei is heterocyclic

Definitions

• the present invention relates to novel chemical compounds, and more specifically, it relates to a new class of phenol phthalein indicator dyes. In a particular aspect it relates to phenol phthaleins useful as optical filter agents in photographic processes for protecting an exposed photosensitive material from post-exposure fogging during development in the presence of extraneous incident light.
• U-.S.' Pat. 6,415,644 discloses a composite photosensitive structure, particularly adapted for use in reflection type photographic diffusion transfer color processes.
• This structure comprises a plurality of essential layers including, in sequence, a dimensionally stable opaque layer; one or more silverhalide emulsion layers having associated therewith dye image-providing material which is radiation and processed by interposing, intermediate the silver halide emulsion layer and the reception layer, an alkaline processing composition providing the first pH and containing a light-reflecting agent, for example, titanium dioxide to provide a white background.
• a light-reflecting agent for example, titanium dioxide
• the light reflecting agent (referred to in said patent as an opacifying agent) also performs an opacifying function, i.e., it is effective to mask the developed silver halide emulsions and also acts to protect the photoexposed emulsions from postexposure fogging by light passing through the transparent layer if the photoexposed film unit is removed from the camera before image formation is complete.
• the composite photosensitive structure includes a rupturable container, retaining the alkaline processing composition having the first pH and light-reflecting agent, fixedly positioned extending transverse a leading edge of the composite structure in order to efiFect, upon application of compressive pressure to the container, discharge of the processing composition intermediate the opposed surfaces of the reception layer and the next adjacent silver halide emulsion.
• the liquid processing composition distributed interme-' diate the reception layer and the silver halide emulsion permeates the silver halide emulsion layers of the composite photosensitive structure to initiate development of the latent images contained therein resultant from photoexposure.
• dye image-providing material associated with each of the respective silver halide emulsion layers is individually immobilized as a function of the point-topoint degree of the respective silver halide emulsion layer photoexposure, resulting in imagewise distributions of mobile dye image-providing materials adapted to transfer, by diffusion, to the reception layer to provide the desired transfer dye image.
• a sufiicient portion of the ions of the alkaline processing composition transfers, by diffusion, to the polymeric neutralizing layer to effect reduction in the alkalinity of the composite film unit to the second pH at which dye image-providing material is substantially nondiffusible, and further dye image-provid-v ing material transfer is thereby substantially obviated.
• the transfer dye image is viewed, as a reflection image, through the dimensionally stable transparent layer against the background provided by the reflecting agent, distributed as a component of the processing composition, intermediate the reception layer and next adjacent silver halide emulsion layer.
• the thus-formed stratum effectively masks residual dye image-providing material retained in association with the developed silver halide emulsion layer subsequent to processing.
• an organic light-absorbing reagent such as a dye, which is present as a light-absorbing species at the first pH and which may be converted to' a substantially nonlight-absorbing species at the second pH is used in conjunction with the light-refiecting agent to protect the selectively exposed silver halide emulsions from post-exposure fogging when development of the photoexposed emulsions is conducted in the presence of extraneous incident actinic radiation impinging on the transparentlayer of the film unit.
• an organic light-absorbing reagent such as a dye
• pH-sensitive dyes derived from certain hydroxy-substituted carbocyclic aryl compounds, viz., particular phenols and naphthols are disclosed as useful as optical filter agents for absorbing incident radiation actinic to selectively exposed photosensitive materials within a predetermined wavelength range in the longer wavelength region of the visible spectrum.
• novel dyes disclosed therein namely indicators which contain a carboxy-phthalide or naphthalide as the ring-closing moiety bonded to two p-hydroxyphenyl radicals each substituted with a hydrogen-bonding group are among the indicator dyes comprising the subject matter of the present invention.
• Such dyes find particular utility as optical filter agents in photographic processes employing highly alkaline processing solutions.
• the invention accordingly comprises the processes involving the several steps and the relation and order of one or more of such steps with respect to each of the others, and the products and compositions possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
• phenol indicator dyes which contain as the ring-closing moiety, a naphthalide or a carboxy phthalide possessing at least one carboxy group in the 4- and/ or 7-position including dyes wherein the phenol radicals are substituted with hydrogen-bonding groups, which dyes will be defined with greater particularity hereinafter.
• the indicator dyes of the present invention like phthalein indicators in general such as phenol phthalein and phenol naphthalein, possess spectral absorption characteristics which are reversibly alterable in response to changes in environmental pH. These dyes possess a highly colored form capable of absorbing visible radiation in alkaline media at a first pH value above their respective pKa and a substantially colorless form, i.e., a form which is substantially non-light-absorbing in the visible spectrum in less alkaline media at a second pH value below their respective pKa.
• pKa is meant the pH at which about 50% of the dye is present in its light-absorbing form and about 50% is present in its non-light-absorbing form.
• phthalein indicator dyes are commonly employed, for example, to measure changes in pH value as reflected by the change in color of the dye from one color to another or from colored to colorless or vice versa.
• the indicator dyes of the present invention compared to the phthaleins in general use possess one or more properties in addition to their color-changing characteristics which render them useful as optical filter agents in photographic processes performed under alkaline conditions, such as those described above.
• phenol indicator dyes which contain a napthalide ring-closing moiety exhibit good stability 'in aqueous alkali in comparison to phenol indicator dyes which contain a simple, i.e., unsubstituted phthalide group as the ring-closing moiety.
• the latter indicators tend to be unstable in alkali and in strongly alkaline media tend to lose color quite rapidly.
• these phthalide indicatordyes mayberenderedstable in alkaline media like the naphthalides bysubstituting a carboxy group in the 4- and/ or 7-position of the phthalide ring.
• the pKa of phenol phthalidesnndhaphthalides in general i.e., the pKa that generates color
• the indicator dyes of the present invention maybe represented by the formula:
• a and B are selected from two I radicals and two radicals wherein R is a hydrogen-bonding group having a negative charge in basic solution and X representsthe' atoms necessary to complete a' ring-closing" moiety selected from a naphthalideand a phthalide substituted. with a carboxy group in at least one of the 4- and 7-posijtions, said A and B radicals being when X represents a naphthalideaThesrespectivenaphe thalide and carboxyphthalide ring-closing moieties are illustrated below: 7
• any hydrogenabon'ding group may be used that is capable of raisingthe:pKa.
• the heteroatom in the hydrogen-bonding group has attached to it a proton which is more acidic than the proton on the phenolic OH and ionizes in basic solution to a negative charge.
• Such groups include, for example, carboxy; hydroxy; o-hydroxyphenyl; bis trifiuo'romethyl carbinol; sulfonamido NHSO R wherein R may be alkyl, aryl, alkaryl); and sulfamoyl (SO -NHR' wherein R may be alkyl, aryl, alkaryl)
• Suitable R and R' substitutents include branched or straight chain alkyl, e.g., methyl, ethyl, isopropyl, n-butyl, t-butyl, hexyl, octyl, dodecyl, hexadecyl, octadecyl and eicosanyl; aryl, e.g., phenyl and naphthyl; and alkaryl, e.g., benzyl, phenethyl, phenylhexyl,
• compounds containing a sulfamoyl or sulfonamido substituent afford the distinct advantage of allowing the immobilizing function to be combined with the hydrogen bonding function by selecting sulfonamido or sulfamoyl (SO NHR') groups containing as R or R an immoblizing group, such as, hexadecyl or pdodecylphenyl.
• the compounds represented in the above formula may contain substitutents other than those specified.
• the A and/or B radicals may contain additional substituents and likewise, the ringclosing moiety may contain other substituents as may be desired.
• pKa pKa
• aryl such as, phenyl and naphthyl
• alkaryl such as, benzyl, phenethyl, phenylhexyl, and p-dodecylphenyl
• alkoxy such as, methoxy, ethoxy, butoxy, l-ethoxy-2-(fl-ethoxyethoxy) and octadecyloxy
• aryloxy such as phenoxy, benzyloxy and naphthoxy
• alkoxyalkyl such as methoxyethyl, eth
• phenol indicator dyes within the scope of the present invention are as follows:
• Phthalein dyes including naphthalides and carboxy-phthalides may be prepared by reacting the appropriate anhydride or acid chloride, e.g., naphthalic or hemimellitic anhydride with the selected phenol at elevated temperatures usually in the presence of a suitable catalyst, such as a Lewis acid catalyst.
• a suitable catalyst such as a Lewis acid catalyst.
• Another method of preparing these phthaleins comprises reacting the selected phenol with naphthalaldehydic or carboxyphthalaldehydic acid in the presence of a mild acid catalyst, e.g. toluene-p-sulfonic acid, to yield the corresponding (na)phthalidyl-substituted intermediate which is oxidized by treating with dichlorodicyanoquinone or other suitable oxidizing agent. The oxidized intermediate is then reacted with another mole of the selected starting phenol in the presence of an acid catalyst to yield the desired dye.
• a mild acid catalyst e.g. toluene-p-sulfonic acid
• EXAMPLE 6 Preparation of the compound of formula (14)
• the compound prepared in Example 5 (1.68 gms., 0.0035 mole) was dissolved in 25 ml. of the ethyl acetate and 25 ml. of dichloromethane in a Parr bottle. To this was added 5% palladium on carbon, and the solution was shaken for 16 hours with 40 lbs. of hydrogen. After the theoretical amount of hydrogen Was consumed, p-dodecylbenzenesulfonyl chloride (2.50 gms., 0.0072 mole) in 37 ml. of acetone was added to the Parr bottle followed by 2 ml. of pyridine. The reaction mixture was then shaken at 26 C.
• the resulting brownish-orange gum was taken up in dichloromethane and put on a dichloromethane-silica gel column. Elution with dichloromethane and with 3% acetone-dichloromethane removed several bands of impurities. Increasing to 5% acetone-dichloromethane removed the product. The solution containing the product was evaporated to give a yellow glass which was taken up in just enough dichloromethane to dissolve. The product was precipitated with hexane, filtered, and dried to give the title compound, an off-white solid (1.138 gms., melting range 9496 C.).
• EXAMPLE 8 Preparation of the compound ofjform "a (27) Aluminum trichloride (4.0 gms.) was added to a solution of biphenol (6.0 gms.) intetrachloroethane (15 ml.) with stirring. The solution was-brought to reflux and 3,3- dichloronaphthalide (2.5 gins. )"in tetrachloroethane (10 ml.) was added dropwise over-about an hour. The red solution was stirred at reflux overnightand poured hot onto ice/water. A yellowish gum separated which was steam distilled. The cdoled mixture ofgum rny solid-water was partitioned between water-chloroform.
• EXAMPLE 10- Preparation of the compound of formula (25)
• EXAMPLEtl Preparation of'the compoiiiid of formula (9) if desired, or the 7-carb.oxyphthalide may be isolated from .the initial precipitate from the reaction mixture by recrystallization as detailed in Example 1.
• the indicator dyes of the present invention exhibit good stability in alkaline media.
• the enhanced stability in alkali has been demonstrated by determining color retention of the dyes in strong aqueous alkali.
• the respective dyes were dissolved in 2M aqueous sodium hydroxide andthe color of each solution measured spectrophotometrically immediately upon mixing and again after ten minutes to determine if any decolorization occurred upon standing.
• biphenol phthalein like phenolphthalein decolorized very rapidly in strong alkali with less than 1% color retained after 10 minutes.
• Biphenol carboxyphthalein (Example 9 above) and biphenol naphthalein,(-Example8 above) both showed color retention of 100% after - 10 minutes.
• the biphenol phthalein employed was prepared by reacting biphenol and hemimellitic anhydride; according to the procedure given in Example 1 above.
• the indicator dyes of the preferred embodiment as represented in Formula (H) possess a relatively high pKa of about 11 or more in addition to good alkaline stability.
• phenol, 7-carboxyphthalein (formula 1) and phenol" 4-carboxyphthalein (formulal20) both have a pKa of about 9.6.
• any of the indicatopdyes of the present invention due to their alkaline stability are suitable for use as optical filter agents in photographic processes where development of a photosensitive material is conducted in the presence of extra neofis incident ligl tr '
• the dyes described above have a highly colored, light absorbing form in alkaline media at a pH above their respective pKa and'a substantially colorless form, i.e., a form whichis'substantially non-light-absorbing in the visible region in less alkaline media at a pH below their respective pKa.
• an indicator dye or dyes ni'aybe selected'from the aforementioned class of compounds which will be in a colored or light-absorbing form at the particular pH employed during development and which may be converted to a substantially non-light-absorbing form subsequent to at least the initial stages of development to permit viewing of the final image.
• the optical filter agent In photographic processes where the optical filter agent is retained in association with the final image formed, it may be readily converted to a form which does not interfere with viewing of the image and which does not detract from the brilliance, hues and other properties of the image.
• the present invention pro-' vides indicator dyes that are particularly useful in diffusion transfer processes and especially in diffusion transfer photographic processes employing composite photosensitive elements such as those described in aforementioned US. Pat. 3,415,644.
• a highly alkaline processing composition having a pH of 13-14 or higher is employed so that it is desirable to use an optical filter agent having a pKa of 11 or preferably 12 or higher that will provide protection from incident actinic radiation during the processing interval but subsequent to the initial stages of the development may be rapidly converted to its colorless form to permit early viewing of the final image.
• the indicator dyes used as the optical filter agents may be initially disposed in a layer of the composite film unit but preferably are initially disposed in the processing composition applied subsequent to selective photoexposure of the photosensitive structure.
• the dyes selected When incorporated into the processing composition, it is desirable that the dyes selected exhibit good stability in highly alkaline media in addition to efiicient absorption in the visible spectrum and a high pKa.
• the, dyes employed as optical filter agents are preferably substantially non-dilfusible in the alkaline processing composition in order to achieve optimum efiiciency as a radiation filter and to prevent diffusion of filter agent into layers of the film unit where its presence may be undesirable.
• Indicator dyes which possess these preferred characteristics are those represented in Formula (H). These indicator dyes possess the desired unique combination of properties, namely, (1) efiicient absorption of actinic radiation within the wavelength range of about 500 nm. to 700 nm., (2) a high pKa of 11 or more, (3) stability in highly alkaline media, and optionally, (4) non-diifusibility in aqueous alkali. As noted above, the photographic use of these dyes as optical filter agents in photographic processes is disclosed and claimed in copending US. Pat. Application Ser. No. 103,392 filed concurrently herewith.
• a and B are the-same and are selected from two radicals and two on a R radicals wherein R is a hydrogen-bonding group selected from hydroxy, carboxy, o-hydroxyphenyl, sulfonamido and sulfamoyl; -R' is selected from hydrogen, methoxy and alkyl having 1 to 3 carbon atoms; R" is selected from hydrogen, methoxy, N and NH R" is selected from hydrogen, methoxy and alkyl having 1 to 3 carbon atoms; and X represents the atoms necessary to complete a ring-closing moiety selected from naphthalide and phthalide substituted with at least one carboxy group in at least one of the 4- and 7-positions, said A and B radicals being when X represents naphthalide.
• a and B are the same and are selected from two 10 radicals and two 011 I ORII III radicals wherein R is a group containing a heteroatom possessing an active unshared pair of electrons selected from O, N and S, said heteroatom possessing a proton more acidic than the proton of the adjacent OH and ionizing to a negative charge in basic solution to form an intramolecular hydrogen bond with said -0H, said group forming a 5-, 6- or 7-membered hydrogen-bonded ring with said OH; R is selected from hydrogen, methoxy and alkyl having 1 to 3 carbon atoms; R" is selected from when X represents naphthalide.

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• 1971
  • 1971-01-04 US US103392A patent/US3702245A/en not_active Expired - Lifetime
  • 1971-01-04 US US00103864A patent/US3833615A/en not_active Expired - Lifetime
  • 1971-01-04 US US00103865A patent/US3833614A/en not_active Expired - Lifetime
  • 1971-05-28 GB GB100874A patent/GB1363870A/en not_active Expired
  • 1971-05-28 GB GB1798971A patent/GB1363864A/en not_active Expired
  • 1971-05-28 GB GB1799671A patent/GB1363866A/en not_active Expired
  • 1971-05-28 GB GB1799471A patent/GB1363865A/en not_active Expired
  • 1971-06-03 CH CH806471A patent/CH616008A5/de not_active IP Right Cessation
  • 1971-06-04 BE BE768108A patent/BE768108R/fr active
  • 1971-06-04 BE BE768109A patent/BE768109A/fr not_active IP Right Cessation
  • 1971-06-04 CA CA114,884A patent/CA953731A/en not_active Expired
  • 1971-06-04 BE BE768107A patent/BE768107A/fr not_active IP Right Cessation
  • 1971-06-04 AT AT488471A patent/AT322979B/de not_active IP Right Cessation
  • 1971-06-04 DE DE19712165998 patent/DE2165998A1/de active Granted
  • 1971-06-04 FR FR717120371A patent/FR2094078B1/fr not_active Expired
  • 1971-06-04 DE DE2166141A patent/DE2166141C3/de not_active Expired
  • 1971-06-04 FR FR717120370A patent/FR2111648B2/fr not_active Expired
  • 1971-06-04 CA CA114,883A patent/CA953730A/en not_active Expired
  • 1971-06-04 DE DE19712127818 patent/DE2127818A1/de not_active Withdrawn
  • 1971-06-04 CA CA114,885A patent/CA973416A/en not_active Expired
  • 1971-06-04 FR FR717120372A patent/FR2094079B1/fr not_active Expired
  • 1971-06-07 NL NLAANVRAGE7107766,A patent/NL169111C/xx not_active IP Right Cessation
  • 1971-06-07 NL NLAANVRAGE7107767,A patent/NL168958C/xx not_active IP Right Cessation
  • 1971-06-07 NL NLAANVRAGE7107765,A patent/NL169110C/xx not_active IP Right Cessation

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