US3291607A - Water-soluble polyoxyalkylenated butyne-2-diol-1, 4 development accelerators - Google Patents

Water-soluble polyoxyalkylenated butyne-2-diol-1, 4 development accelerators Download PDF

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Publication number
US3291607A
US3291607A US459872A US45987265A US3291607A US 3291607 A US3291607 A US 3291607A US 459872 A US459872 A US 459872A US 45987265 A US45987265 A US 45987265A US 3291607 A US3291607 A US 3291607A
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United States
Prior art keywords
development
butyne
diol
water
developer
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Expired - Lifetime
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US459872A
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English (en)
Inventor
Dersch Fritz
Betty D Fadden
William L Wike
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GAF Chemicals Corp
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General Aniline and Film Corp
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Publication date
Application filed by General Aniline and Film Corp filed Critical General Aniline and Film Corp
Priority to US459872A priority Critical patent/US3291607A/en
Priority to DE19661547906 priority patent/DE1547906A1/de
Priority to GB22262/66A priority patent/GB1139098A/en
Priority to BE681581D priority patent/BE681581A/xx
Priority to NL6607274A priority patent/NL6607274A/xx
Priority to FR63163A priority patent/FR1481444A/fr
Application granted granted Critical
Publication of US3291607A publication Critical patent/US3291607A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/305—Additives other than developers
    • G03C5/3056—Macromolecular additives

Definitions

  • the so-called high energy developers heretofore provided i.e., those which yield maximum density levels in reduced periods of development time have, in many instances, provided only marginal advantage over the more mildly acting developer compositions.
  • the high speed developers currently known pose serious problems such as excessive fog and graininess, as well as a general softening in the photographic emulsion developed therewith.
  • the eifect of fogging is to increase the overall density of the negative obtained and to depress the contrast of the image in the less exposed areas.
  • the fogging density produced is greater in the case of high speed emulsions and becomes more pronounced with increased development time and/ or temperature. Consequently, considerable difficulty is often encountered in obtaining proper gradation and especially within the time interval prescribed for development.
  • a primary object of the present invention resides in the provision of improved photographic developers wherein the above disadvantages are eliminated or at least mitigated to a substantial degree.
  • Another object of the present invention resides in the provision of improved photographic developers possessing outstanding speed and fine-grain characteristics.
  • a further object of the present invention resides in the provision of improved developer compositions which exhibit little or no tendency to fog silver halide emulsions developed therewith.
  • a still further object of the present invention resides in the provision of improved developer compositions characterized by a siginficant decrease in the induction period required for photographic development therewith.
  • One of the truly outstanding features characterizing the discovery forming the basis of the present invention relates to the fact that developer compositions modified in accordance therewith enable the attainment of effective film speeds substantially in excess, i.e., on the order of 50% and higher of the optimum speed ordinarily obtainable by virtue of the particular silver halide emulsion and/ or developer employed.
  • 1,4-butyne diol polyoxyalkylenated derivatives contemplated for use in accordance with the present invention can be conveniently represented according to the following structural formula:
  • alkylene oxide adducts encompassed by the above formula may be prepared according to procedures well established in the art such as those described in United States Patents 1,970,578; 2,213,477; 2,575,832; 2,593,112 and 2,676,975.
  • a selected 1,4-butyne diol can be reacted with one or more alkylene oxides in the presence of a small amount of catalyst usually an alkaline catalyst such as sodium hydroxide at atmospheric or super-atmospheric pressure employing elevated temperatures ranging from e.g., about 100 to 200 C.
  • the reaction can be conducted in the presence of an inert solvent and to the extent desired conventional heat transfer means can be employed to remove the heat of reaction.
  • the amount of alkylene oxide employed in the reaction will depend upon the average molecular weight of the product desired.
  • the 1,4-butyne diol is treated with the alkylene oxide until each hydroxyl hydrogen contains at least one mole of ethylene oxide in accordance with the above formula.
  • the addition of the alkylene oxide to each hydroxyl group can be balanced or unbalanced, i.e., each may contain approximately the same or different average number of oxyalkylene groups per chain.
  • the molecular weight of the polyoxyalkylenated 1,4-hutyne diol depends upon the amount of ethylene oxide utilized in the reaction and can be readily determined by analysis of hydroxyl content.
  • the hydroxyl number is a measure of and is proportional to the hydroxyl concentration per unit of weight.
  • the hydroxyl number is defined in terms of milligrams of potassium hydroxide equivalent per gram of the 1,4-butyne diol reaction product, and is determined by reacting acetic anhydride (in pyridine solution) at refluxing temperature with the hydroxyl groups of the alkylene oxide-1,4-butyne diol reaction product.
  • the unreacted anhydride and acetic acid formed are back-titrated with aqueous sodium hydroxide using phenolphthalein as an indicator.
  • the molecular weight can be readily calculated from the hydroxyl number according to the following formula:
  • the amount of water-soluble polyoxyalkylenated 1,4- butyne diol employed in the developer composition is not especially critical and accordingly, may vary over a wide range. In this regard, it has been found that amounts ranging from as little as 0.25 grams up to 30 grams and higher per liter of developer composition are particularly beneficial. Proportions substantially in excess of the aforementioned would not ordinarily be warranted since the attendant improvement would, in many instances, be offset by the increased costs involved. Within the concentration ranges recommended, it is found that the above compounds provide speed increases on the order of 50% and higher than can be expected with the use of conventional developer compositions of the type currently available.
  • the polyoxyalkylenated butyne diols contemplated for use in accordance with the present invention must conform to two essential requirements namely, they must (1) be water soluble, and (2) contain a total of at least 7 combined alkylene oxide units.
  • the question of watersolubility assumes considerable significance in connection with compounds encompassed by the above formula wherein one or more of the pendant R groups is alkyl. As will be readily apparent, as the number of carbons is increased, the compound becomes correspondingly more hydrophobic. However, within the limitation expressed in the above formula it is found that the desired degree of water-solubility is obtained regardless of the hydrophobicity introduced as a result of the p endant alkyl substituents, if the number of combined alkylene oxide units is at least 7. For example, it is found that compounds containing less than the prescribed minimum of combined alkylene oxide units do not possess the requisite solubility in aqueous developer solutions and tend to yield an undesirable scum.
  • the alkylene oxide units comprise at least 60% and more preferably from to 95% of the butyne diol derivative.
  • the amount of combined alkylene oxide units may exceed the aforestated maximum sinceall of the derivatives within this range possess the requisite solubility in silver halide developer compositions.
  • the polyoxyalkylenated 1,4-butyne diols contemplated for use herein fall within a range of from about 400 up to several thousand, i.e., on the order of l0-11,000. Particularly beneficial results are obtained however, with derivatives having molecular weights within the range of from about 900 to about 5,000.
  • the sum of m and n in the above formula can have an average value ranging from about 7 to about 250 with a range of about 15 to about 100 being preferred.
  • the higher molecular weight materials are obtained in the form of waxy, amorphous solids.
  • no particular difficulty is encountered in forming aqueous solutions therewith since the combined alkylene oxide units are sufficient to provide the necessary water-solubility.
  • the materials encompassed by the above formula are available commercially from the Air Reduction Chemical and Carbide Company, a Division of Air Reduction Company, under the trade name Surfynol. Such products are identified according to a numerical code number which indicates the percentage of combined ethylene oxide units, e.g., Surfynol 485 and Surfynol 495 connote compounds of the above formula containing respectively, and combined ethylene oxide.
  • the excellent water-solubility of the butyne diol derivatives of the present invention assures thorough and uniform distribution thereof throughout the emulsion which, of course, in the case of a multi-layer color element is of primary import in achieving good color balance.
  • the improvements provided by the present invention are not dependent upon the use of any particular type of silver halide developer. Accordingly, the latter may be of the hydroquinone type, i.e., those which contain hydroquinone, potassium metabisulfite and potassium bromide, or they may be of the metolhydroquinone type, i.e., those which contain p-methylaminophenol, sodium sulfite, sodium bisulfite, hydoquinone, sodium carbonate, and potassium bromide.
  • the developer composition may be of the so-called borax type, i.e., those which contain p-methylaminophenol, sodium sulfite, hydroquinone, borax and potassium bromide.
  • borax type i.e., those which contain p-methylaminophenol, sodium sulfite, hydroquinone, borax and potassium bromide.
  • the 1,4-butyne diol polyoxyalkylenated derivatives of the present invention find exceptional utility and provide particularly beneficial results when added to black and White developer compositions intended for use in connection With the reversal process of color photography.
  • the latter process involves the formation of color component images in each of a plurality of super-imposed light-sensitive silver halide emulsion layers each containing a non-diffusing color former by a first development of exposed silver halide whereby silver images only are formed, followed by re-exposure and a second development to form silver images and dye images in situ in the reverse image areas of the emulsion layers.
  • the developed film is then fixed and washed in conventional manner.
  • a second sample of the same film is subjected to identical exposure.
  • the exposed film is treated for 5 minutes with the above developer composition further provided with 4 cc. of polyoxyalkylenated 1,4-dimethyl-1,4-diisobutyl-1,4-butyne diol containing 75% combined ethylene oxide units.
  • the relative speed obtained in the case of the conventional, i.e., unmodified developer is 100 whereas the speed obtained with the butyne diol derivative-containing developer is 150.
  • the increase in speed did not entail any significant changes in clearness, gamma or D-Max.
  • the film was then hardened for 3 minutes in a 30% aqueous solution of potassium chrome alum, washed for 3 minutes and given a reversal exposure for 1 minute at 1 foot distance from a No. 2 Photoflood lamp.
  • the developed film was short-stopped for 3 minutes in a bath of the following composition: Sodium acetate gms 20 Acetic acid cc 10 Water tomake 1 liter.
  • the short-stopped film was hardened for 5 minutes in a 3% aqueous solution of potassium chrome alum.
  • Example 7 EXAMPLE In Example II is repeated except that the amount of polyoxyethylenated 1,4-butyne diol included in the modified black and white developer is increased to cc.
  • the reversal image obtained in the three sensitized layers was measured and it was found that the effective increase in the speed in each such layer'was at least 0.4-5 log E greater than that obtained with the film sample which had been treated with the unmodified black and white developer.
  • Example II the noted improvement in film speed was obtained without any attendant adverse effects on the emulsion fog characteristic and/or the photographic quality of the image produced, i.e., clearness, contrast, and the like.
  • the results of Example II are particularly significant. As indicated therein, marked improvement in film speed was obtained in the case of the modified black and white developer, as manifested by the density measurement results, despite the fact that the developing time was only one-third of that required in the case of the unmodified black and white solution.
  • compositions modified in accordance with the teachings of the present invention greatly accelerate the processing of photographic film to an extent heretofore unattainable.
  • the commercial significance of such a process from an economic standpoint alone would be of considerable magnitude.
  • alkylated butyne diol derivatives e.g., polyoxyalkylenated 1,4-dimethyl1,4-diisobutyl-1,4-butyne diol
  • alkylene oxide contents having an average value of at least about and up to 30 and higher.
  • polyoxyalkylenated compounds which result from the reaction of a 1,4-butyne diol compound with mixtures of ethylene oxide and propylene oxide. Accordingly, such materials are to be regarded as equivalents to those more specifically described hereinabove.
  • R is selected from the group consisting of ethylene and propylene and R R R and R are independently selected from the group consisting of hydrogen and lower alkyl and wherein m and n represent positive integers the sum of which has a minimum average value of at least 7.
  • n and n represent positive integers the sum of which has an average value of 7 to 100.
  • halide developing agent in the presence of a water-soluble 1,4-butyne diol derivatives may be effectively employed i in the form of their mixtures, i.e., two or more derivatives containing different percentages of combined alkylene oxide. Further-more, the improvements provided by the present invention are likewise obtained with the use of polyoxyalkylenated butyne-2-diol-1,4 of the formula:
  • Liand propylene and R R R and R are independently selected from the group consisting of hydrogen and lower alkyl and wherein m and I: represent positive integers the sum of which has a minimum average value of at least 7.
  • n and n represent positive integers the sum of which has an average value of 7 to 100.
  • a reversal process of photography in which an exposed photographic element having at least one lightsensitive silver halide emulsion layer containing a nonditfusing color former is (a) given a first development in an aqueous alkaline developing solution containing a silver halide developing agent to form silver images only, (13) re-exposed to light, (0) given a second development in an aqueous developer solution containing a primary aromatic amino color developing agent to form both silver and dye images in the reverse areas of said emulsion layer; said process being characterized in that the first development is carried out in the presence of a development accelerator comprising water-soluble polyoxyalkylenated butyne-2-diol-1,4 of the formula:
  • R is selected from the group consisting of ethylene and propylene and R R R and R are independently selected from the group consisting of hydrogen and lower alkyl and wherein m and n represent positive integers the sum of which has a minimum average of at least 7.
  • n and n represent positive integers the sum of which has an average value of 7 to 100.
  • a process according to claim 9 wherein said silver halide developing agent comprises hydroquinone.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US459872A 1965-05-28 1965-05-28 Water-soluble polyoxyalkylenated butyne-2-diol-1, 4 development accelerators Expired - Lifetime US3291607A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US459872A US3291607A (en) 1965-05-28 1965-05-28 Water-soluble polyoxyalkylenated butyne-2-diol-1, 4 development accelerators
DE19661547906 DE1547906A1 (de) 1965-05-28 1966-05-18 Photographischer Entwickler
GB22262/66A GB1139098A (en) 1965-05-28 1966-05-19 Improvements in or relating to photographic developers
BE681581D BE681581A (en)) 1965-05-28 1966-05-25
NL6607274A NL6607274A (en)) 1965-05-28 1966-05-26
FR63163A FR1481444A (fr) 1965-05-28 1966-05-26 Révélateurs photographiques à développement accéléré par du butyne diol-1, 4-polyoxyalcoylène

Applications Claiming Priority (1)

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US459872A US3291607A (en) 1965-05-28 1965-05-28 Water-soluble polyoxyalkylenated butyne-2-diol-1, 4 development accelerators

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US3291607A true US3291607A (en) 1966-12-13

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BE (1) BE681581A (en))
DE (1) DE1547906A1 (en))
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2648839A1 (de) * 1975-10-27 1977-04-28 Fuji Photo Film Co Ltd Farbphotographisches verfahren
US4256830A (en) * 1977-11-22 1981-03-17 Agfa-Gevaert, A.G. Photographic material containing a stabilizer
USH1020H (en) 1989-09-25 1992-02-04 Konica Corporation Developing solution for light-sensitive silver halide photographic material and method of forming photographic image making use of it
WO2001004178A1 (en) * 1999-07-09 2001-01-18 The Dow Chemical Company Polymerization of alkylene oxides using metal cyanide catalysts and unsaturated initiator compounds

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2648839A1 (de) * 1975-10-27 1977-04-28 Fuji Photo Film Co Ltd Farbphotographisches verfahren
US4066461A (en) * 1975-10-27 1978-01-03 Fuji Photo Film Co., Ltd. Color photographic process
US4256830A (en) * 1977-11-22 1981-03-17 Agfa-Gevaert, A.G. Photographic material containing a stabilizer
USRE31514E (en) * 1977-11-22 1984-01-31 Agfa-Gevaert Aktiengesellschaft Photographic material containing a stabilizer
USH1020H (en) 1989-09-25 1992-02-04 Konica Corporation Developing solution for light-sensitive silver halide photographic material and method of forming photographic image making use of it
WO2001004178A1 (en) * 1999-07-09 2001-01-18 The Dow Chemical Company Polymerization of alkylene oxides using metal cyanide catalysts and unsaturated initiator compounds
US6355845B1 (en) 1999-07-09 2002-03-12 The Dow Chemical Company Polymerization of alkylene oxides using metal cyanide catalysts and unsaturated initiator compounds

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DE1547906A1 (de) 1969-12-18
GB1139098A (en) 1969-01-08
NL6607274A (en)) 1966-11-29
BE681581A (en)) 1966-10-31

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