US3679421A - Azo dye-forming system including a boric acid ester - Google Patents

Azo dye-forming system including a boric acid ester Download PDF

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US3679421A
US3679421A US853028A US3679421DA US3679421A US 3679421 A US3679421 A US 3679421A US 853028 A US853028 A US 853028A US 3679421D A US3679421D A US 3679421DA US 3679421 A US3679421 A US 3679421A
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boric acid
acid ester
radical
diazo
hydroxy
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George P Kasper
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Eastman Kodak Co
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Eastman Kodak Co
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    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/52—Compositions containing diazo compounds as photosensitive substances
    • G03C1/61—Compositions containing diazo compounds as photosensitive substances with non-macromolecular additives

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  • This invention is related to photography and is concerned particularly with novel, two-component diazotype compositions which provide increased resistance to premature coupling upon storage and permit an increased development rate.
  • Two-component diazotype reproduction media normally comprise a polymeric matrix containing at least one diazonium salt and at least one coupler compound which reacts with the diazonium salt, typically in an alkaline medium, to form an azo dye.
  • various other additives such as ultraviolet absor bers, stabilizers to prevent premature coupling of the diazonium salt and the coupler as well as additional known addenda.
  • These diazotype compositions or azo dye-forming systems have been employed generally as duplicating media. Their use typically involves an imagewise exposure to activating radiation, e.g., light, through an original, whereby the transmitted light decomposes the diazonium salt.
  • the iilm After exposure the iilm is usually treated with a basic medium, such as aqueous ammonia vapor, to promote coupling of the undecomposed diazonium salt and coupler compound, thereby forming an azo dye in the unexposed areas to provide a positive image corresponding to that of the original.
  • a basic medium such as aqueous ammonia vapor
  • Another object of the present invention is to provide a novel light-sensitive azo dye-forming system which exhibits both an increased resistance to premature coupling and an increased development rate.
  • Still an additional object of the instant invention is to provide a new light-sensitive azo dye-forming system containing a boric acid ester to promote increased resistance to premature coupling and an increased develop ment rate.
  • Yet another object of the present invention is to provide a novel two-component diazotype composition containing a boric acid ester both to inhibit premature coupling and to promote rapid development.
  • a diazotype composition which is useful as an image reproduction medium and which includes at least one lightsensitive diazonium salt, at least one coupler compound which can react with the diazonium salt to form an azo dye, as a combined precoupling inhibitor-development accelerator, at least one boric acid ester.
  • the boric acid esters used in the present diazonium compositions include the esterification products of boric acid and at least one hydroxylated organic compound such as an alcohol which is advantageously an aliphatic or aromatic monoor polyhydroxylic compound with monoand dihydroxy alcohols and glycols being favored.
  • the boric acid esters useful herein can be desirably substituted, but it is preferred that they are substituted with other than highly basic substituents such as alkaline nitrogen-containing radicals, so as to preserve the advantageous acidic character of the diazotype composition prior to the desired time of image development, thereby heightening the precoupling restraint promoted by the subject boric acid esters.
  • boric acid esters utilized herein are boric acid triesters of monohydn'c alcohols.
  • Exemplary triesters include those having alkyl ester groups such as cycloalkyl and aliphatic alkyl groups including substituted aliphatic alkyl groups such as aralkyl groups as well as those having aryl ester groups.
  • the ester groups attached to any boric acid molecule can be the same or different and can be composed of various substituent ester groups of the types mentioned immediately hereinabove.
  • ester groups include cycloalkyl radicals having from 4 to 6 carbon atoms in the ring nucleus, aliphatic alkyl radicals having from .1 to 8 carbon atoms in an alkyl chain which can be substituted with radicals including carbon atoms additional to those of the 1 to 8 carbon aliphatic alkyl chain (e.g. aralkyl radicals) and aryl radicals such as phenyl or n'aphthyl radicals. It is understood that the noted cycloalkyl, aliphatic alkyl and aryl ester group radicals are joined to the boric acid moiety through an oxygen linkage.
  • Preferred boric acid esters include such compounds as:
  • boric acid esters which are useful in this invention are advantageously incorporated into diazotype compositions in an amount up to 25 parts by weight per parts by weight of polymeric matrix and preferably between about 5 and 10 parts by weight per 100 parts by weight of polymeric matrix.
  • the diazotype compositions utilized herein typically include a diazonium salt and at least one coupler compound which can react with the diazonium salt to form an azo dye.
  • Advantageous diazonium salts include benzene diazonium salts such as those having the formula:
  • a hydrogen atom (2) a halogen atom, (3) an aryl radical, (4) an amino radical including substituted amino radicals which can be cyclic radicals including the amino nitrogen atom and other hetero atoms such as oxygen, sulfur, nitrogen, etc., (5) a rnercapto radical, or (6) an alkyl or aryl thioether radical, and
  • These compounds can also be substituted on one or more of the nuclear benzene carbons with, for example, at least one of either a halogen atom, an aliphatic alkyl radical, an alkoxy radical, an acyl radical, a carbamyl radical, a carboxyl radical or a nitro radical.
  • Aliphatic alkyl radicals are defined herein to include straight and branched chain alkyl radicals having from 1 to 8 carbon atoms such as methyl, ethyl, isopropyl, tertbutyl, n-amy], octyl and the like.
  • Particularly useful diazonium salts include p-aminobenzenediazonium salts having the formula as described above wherein M is either an amino radical including substituted amino radicals or a thioether radical such as described above, and wherein the benzene nucleus is unsubstituted or substituted in at least one of the 2-position and the 5-position with either an aliphatic alkyl radical or an alkoxy radical.
  • M is either an amino radical including substituted amino radicals or a thioether radical such as described above
  • benzene nucleus is unsubstituted or substituted in at least one of the 2-position and the 5-position with either an aliphatic alkyl radical or an alkoxy radical.
  • This class of useful diazonium salts can be represented by the formula:
  • D is either a sulfur atom or a radical having the formula NR
  • R when taken alone, is either a hydrogen atom when D is NR or a lower aliphatic alkyl radical, a lower alkoxy radical, an acyl radical having the formula wherein T is either an aryl radical or an alkyl radical as described elsewhere herein, or a phenyl radical when D is either a sulfur atom or NR,
  • R when taken alone, is either a hydrogen atom, a
  • Preferred p-aminobenzene diazonium salts include substituted aminobenzene diazonium salts having the formula:
  • each of R and R, when taken alone, is a lower alkyl radical
  • R and R are alkoxy radicals when R and R complete a morpholino radical
  • R and R are each a hydrogen atom when R and R are each a lower alkyl radical.
  • Illustrative of the subject diazonium salts are such compounds as the salts of 1-diazo-2,S-dimethoxybenzene; l-diazo-2,5-diethoxybenzene; l-diazo-4-chloro-2,S-diethoxybenzene; 4idiazo-2,5-dimethoxybiphenyl; 4-diazo-2,5,4'-triethoxybiphenyl; 1-diazo-4-dimethylaminobenzene; l-diazo-4-(diethoxyamino)benzene; 1-djazo-4- [bis (hydroxypropyl)amino1benzene; l-diazol(N-methyl-N-allylamino)benzene; 1-diazo-4-(diamy1amino)benzene; l-diazo-4-(oxazolidino)benzene; 1-diazo-4-'(cyclohexylamino)benzen
  • Azo dye couplers which can be reacted with the diazonium salt to form an azo dye include a wide variety of chemical species such as those disclosed by Kosar, Light-Sensitive Systems, John Wiley & Sons, Inc., New York 1965), pp. 220-240. Phenolic couplers are preferred, however, with particularly preferred classes including:
  • R is a phenyl radical, and preferably a phenyl radical substituted with at least one of either a lower alkyl radical or a lower alkoxy radical or a halogen atom;
  • R is either an alkyl radical or an alkoxy radical and R is an aliphatic alkyl radical, an aryl radical, an aralkyl radical or an aralkoxy radical.
  • lower aliphatic alkyl and alkoxy radicals are deemed to refer to aliphatic alkyl and alkoxy radicals having from 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, isobutyl, tert-butyl and like alkyl radicals as well as alkoxy radicals such as methoxy, ethoxy, propoxy, tert-butoxy and the like.
  • the diazotype composition is generally dispersed in a polymeric matrix such as those described hereinbelow, conventionally in an amount of from about 20 to about 40 parts by weight per parts of matrix polymer.
  • the diazotype composition can contain and usually does contain other additives such as ultraviolet absorbers, stabilizers and the like to advantageously modify its photographic and chemical properties.
  • a preferred class of additives includes the known acid stabilizers which operate to prevent premature coupling of the diazonium salt and coupler compound. These acid stabilizers include organic acids such as S-sulfosalicylic acid and the like.
  • an organic acid stabilizer is preferably present in all of the diazotype reproduction media of this invention, with the amount normally varying from about 1 part to about 6, and preferably from about 2 to about 5 parts by weight per 100 parts of polymeric matrix.
  • metal salts such as zinc chloride can also be present as a development accelerator or dye brightener, generally in an amount of from about 0.5 to about 1.5 parts by weight per 100 parts of matrix polymer.
  • Another, and especially desirable, class of additives for diazotype compositions comprises hindered phenols containing in the 2-position either an alkyl or a cycloalkyl radical and in the 4-position an alkyl radical, an alkoxy radical, a hydroxyl radical or a thioether radical, which with the hindered phenolic moiety completes a hindered bisthiophenol and more generally a symmetrical bisthiophenol.
  • These hindered phenols restrain fading of the developed azo dye image.
  • Such advantageous hindered phenols are described in detail in the copending US. patent application Ser. No. 663,470, filed July 31, 1967, now Patent No. 3,591,381.
  • the diazotype compositions are typically carried in a film-forming hydrophobic polymeric matrix or hinder when preparing photographic elements, both for ease of coating and physical stability of the resultant light-sensitive layer.
  • Advantageous matrix polymers include a wide variety of polymeric substances such as, for example, cellulosic ethers such as ethyl cellulose, butyl cellulose as well as cellulose esters such as cellulose acetate, cellulose triacetate, cellulose propionate, cellulose acetate propionate, cellulose butyrate and cellulose acetate butyrate; vinyl polymers such as poly(vinyl acetate), poly(vinylidene chloride), poly (vinyl butyral), copolymers of vinyl chloride and vinyl acetate, polystyrenes, poly(methyl methacrylate), copolymers of alkylacrylates and acrylic acid, etc.; polyesters such as the esterification product of p-cyclohexanedicarboxylic acid and 2,
  • Photographic elements utilizing the light-sensitive diazotype compositions of this invention are conveniently prepared by coating such a composition onto a support material by means such as immersion, flow coating, whirl coating, brushing, doctor blade coating, hopper coating and the like to prepare a light-sensitive layer.
  • Advantageous support materials include conventional photographic film base materials, for example, cellulose esters such as cellulose acetate, cellulose triacetate, cellulose acetate butyrate, etc., poly a-olefins such as polyethylene and polypropylene, polyesters such as poly(ethylene terephthalate), polystyrenes, polycarbonates, as well as metals such as zinc and aluminum and paper including polyethylene and polypropylene coated papers.
  • Other support materials that are suitable for use herein are known in the art.
  • Coating is typically by solvent coating means, since it offers the potential for rapid, convenient, continuous operation. Coating is'eflected by first dissolving the photographic image-forming composition in a suitable solvent, along with a matrix polymer if desired. Exemplary matrix polymers are described hereinabove.
  • the coating solution conventionally contains from about to about 20 weight percent solids, and preferably from about 8 to about 15 percent solids. In that solution, if a matrix polymer is utilized, the photographic image-forming components are typically included in an amount of from about 20 to about 50 parts by weight per 100 parts of polymeric binder, with concentrations in the range of from about 25 to about 45 parts per 100 parts of matrix polymer being preferred.
  • the coated material After coating by such means as whirl coating, brushing, doctor blade coating, hopper coating or the like, typically at a Wet thickness of from about 25 microns to about 125 microns, the coated material is dried to prepare a composite photographic element of this invention.
  • the diazotype compositions of this invention including a boric acid ester such as those described herein, are advantageouslyrapidly processibleunder a wide variety of proc s sing conditions. Moreover, they exhibit significant resistance to undesirable precoupling, even at elevated temperatures and under high humidity conditions, this resistance being maintained for long periods of time (e.g. 6 months to 1 year).
  • the resultant elements can be imagewise exposed and developed to prepare a positive azo dye image corresponding'to the original.
  • Exposure is typically to a light source rich in ultraviolet rays, such as a mercury arc lamp, a photoflood lamp or the like.
  • Image development is conveniently accomplished by contacting the exposed element with an alkaline medium such as moist ammonia vapor at ambient pressure or high pressure anhydrous ammonia gas, which promotes the reaction ofdiazonium salt and coupler compound to form an azo dye image. No further image stabilization is necessary.
  • EXAMPLE 1 -A light-sensitive diazotype composition is prepared containing the following ingredients:
  • composition is coated using a doctor blade onto a subbed poly(ethylene terephthalate) support material to prepare a photographic element. After drying, the thickness of the light-sensitive layer is about 7.5 microns. Portions of the element so prepared are stored under dark conditions at 21 C. and 100% relative humidity for a A light-sensitive diazotype composition containing the following ingredients is prepared:
  • the composition is coated using a doctor blade apparatus onto a subbed poly(ethylene terephthalate) support to prepare a photographic element. After drying, the lightsensitive layer has a thickness of about 7.5 microns. Portions of this element are then stored under dark conditions at 38 C. and relative humidity for a period of hours. Minimum density of the unexposed portions rises by 0.38 after the storage period. Density measurements are obtained as in Example 1.
  • EXAMPLE 4 A photographic element is prepared according to the procedure of Example 3, except that tricyclohexyl boric acid ester is omitted from the diazotype composition. Af-
  • Example 3 ter storage of samples as in Example 3, the minimum density rises to 0.51, density measurements being obtained as in Example 1.
  • EXAMPLE 5 The unexposed photographic element portions of Examples 1, 2, 3 and 4 are processed by treatment with anhydrous ammonia gas at a temperature of 55 C. in a General Aniline and Film Ozalid Junior Ozamatic Processor.
  • the development rate of the portions from Examples 1 and 3 (containing a boric acid ester) is about twice as rapid as that for the portions from Examples 2 and 4 (boric acid ester omitted).
  • Comparative development rates for the photographic elements of Examples 1 and 2 are summarized below in tabular form, the rates being expressed in percent of developed density as a function of time.
  • Comparative results are obtained with a comparison of elements from Examples 3 and 4.
  • a comparison of the results appearing in the above table is graphically presented in the accompanying drawing.
  • the vertical axis is calibrated for a percentage of the maximum visible difiuse density obtainable in a completely developed element.
  • the horizontal axis is calibrated in seconds corresponding to the development time of each element.
  • the lower plotted curve indicates the development rate of a diazotype composition which does not contain a boric acid ester.
  • the upper plotted curve indicates the increased development rate obtained with a like diazotype composition, but with tricyclohexyl boric acid ester added as a combined pre-coupling inhibitor, development accelerator. It is seen by reference to the graph that the rate of development with the boric acid ester present is significantly accelerated with developed density being increased by a factor of about 2.5 at 24 seconds development time.
  • EXAMPLE 6 The procedures of Examples 1, 2, 3, 4 and 5 are repeated in three separate sets, except that in those elements containing a boric acid ester, the following esters are used in lieu of tricyclohexyl boric acid ester.
  • a diazotype composition consisting essentially of a light-sensitive diazonium salt, a coupler compound which can react with said diazonium salt to form an azo dye, a film-forming, hydrophobic polymeric binder, an acidic stabilizer and, as a combined precoupling inhibitor-development accelerator, a triester of boric acid and a monohydric alcohol.
  • a diazotype composition as described in claim 1 wherein the boric acid triester is selected from the group consisting of trialiphatic alkyl boric acid esters, triaryl boric acid esters and tricycloalkyl boric acid esters.
  • a diazotype composition consisting essentially of a film-forming, hydrophobic polymeric matrix containing therein a light-sensitive diazonium salt, a coupler compound which can react with said diazonium salt to form an azo dye, an acidic stabilizer and as a combined precoupling inhibitor-development accelerator, a boric acid triester selected from the group consisting of:
  • a diazotype composition as described in claim 5 wherein the boric acid triester is selected from the group consisting of a trimethyl boric acid ester, a triethyl boric acid ester, a tripropyl boric acid ester, a triphenyl boric acid ester, and a tricyclohexyl boric acid ester.
  • a diazotype composition consisting essentially of a film-forming, hydrophobic polymeric matrix containing therein a light-sensitive diazonium salt, a coupler compound which can react with said diazonium salt to form an azo dye, an acidic stabilizer and, as a combined precoupling inhibitor-development accelerator, a tricyclohexyl boric acid ester in an amount ranging from 5 to 10 parts by weight per 100 parts by weight of said polymeric matrix.

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  • Physics & Mathematics (AREA)
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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US853028A 1969-08-26 1969-08-26 Azo dye-forming system including a boric acid ester Expired - Lifetime US3679421A (en)

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JP (1) JPS4830482B1 (enrdf_load_stackoverflow)
BE (1) BE755280A (enrdf_load_stackoverflow)
CA (1) CA969014A (enrdf_load_stackoverflow)
DE (1) DE2042395C3 (enrdf_load_stackoverflow)
FR (1) FR2059126A5 (enrdf_load_stackoverflow)
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3881931A (en) * 1972-05-22 1975-05-06 Fuji Photo Film Co Ltd Method for developing black diazotype photographic light-sensitive materials
US4054456A (en) * 1972-04-21 1977-10-18 Fuji Photo Film Co., Ltd. Diazo photographic materials containing 2-hydroxy 3-naphthanilide coupler
US4149888A (en) * 1972-06-26 1979-04-17 Gaf Corporation Transparent photographic masks
US4171222A (en) * 1976-11-22 1979-10-16 Hoechst Aktiengesellschaft Two-component diazotype material

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2310586A1 (fr) * 1975-05-07 1976-12-03 Thomson Brandt Procede de fabrication de supports d'informations lisibles optiquement par variation d'absorption et support ainsi obtenu
FR2455303A1 (fr) * 1979-04-24 1980-11-21 Rhone Poulenc Syst Procede pour la fabrication d'une carte d'identification inviolable comportant des photographies et carte obtenue selon ce procede

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4054456A (en) * 1972-04-21 1977-10-18 Fuji Photo Film Co., Ltd. Diazo photographic materials containing 2-hydroxy 3-naphthanilide coupler
US3881931A (en) * 1972-05-22 1975-05-06 Fuji Photo Film Co Ltd Method for developing black diazotype photographic light-sensitive materials
US4149888A (en) * 1972-06-26 1979-04-17 Gaf Corporation Transparent photographic masks
US4171222A (en) * 1976-11-22 1979-10-16 Hoechst Aktiengesellschaft Two-component diazotype material

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JPS4830482B1 (enrdf_load_stackoverflow) 1973-09-20
FR2059126A5 (enrdf_load_stackoverflow) 1971-05-28
CA969014A (en) 1975-06-10
DE2042395C3 (de) 1974-09-05
GB1306127A (enrdf_load_stackoverflow) 1973-02-07
DE2042395A1 (de) 1971-03-11
BE755280A (fr) 1971-02-01
DE2042395B2 (de) 1974-02-14

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