US3887370A - Dye transfer acceleration with polyamine compounds - Google Patents

Dye transfer acceleration with polyamine compounds Download PDF

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US3887370A
US3887370A US320822A US32082273A US3887370A US 3887370 A US3887370 A US 3887370A US 320822 A US320822 A US 320822A US 32082273 A US32082273 A US 32082273A US 3887370 A US3887370 A US 3887370A
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dye transfer
dye
color
layer
development
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Yasushi Ohyama
Hideo Sumitani
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Mitsubishi Paper Mills Ltd
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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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/42—Structural details
    • G03C8/52—Bases or auxiliary layers; Substances therefor
    • 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
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds

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  • This invention relates to an improvement in a known photographic process to which a color development dye transfer method has been applied for obtaining a monochromatic or polychromatic color photograph quickly and simply, and the invention aims to accelerate the development dye transfer rate of the process, to complete the color development dye transfer treatment in a short period of time, and to obtain a beautiful color photographic image excellent in gradation.
  • the color development dye transfer method according to the present invention differs from the conventional color development in the specificity of the color couplers used and in the utilization of a dye transfer layer containing a mordant for an anionic dye.
  • Non-diffusible color couplers of one type are such that a so-called ballast group containing a long chain group has been introduced into the coupling position of a molecule of a known color coupler through a diazo, sulfo, methine or the like group which may be cut by coupling, and sulfone or carboxyl group have been introduced into other position.
  • These couplers individually forrn cyan and magenta diffusible dyes as shown below.
  • Non-diffwi'cle coupler splitting (Developing agent I (Non-diffusib la phenazine "lye I ZAg ZHX ⁇ Dlffusible crap '5 colored aye)
  • This example is specific in that it forms a phenazine dye, but is identical with the aforesaid example in that the portion separated by coupling becomes an anionic diffusible dye, and hence utilized in the present invention.
  • the anionic dye thus formed is a kind of acid dye, and hence diffuses in an aqueous medium.
  • a suitable mordanting agent has been incorporated into a transfer layer which may be situated adjacent to the photosensitive emulsion layer, the said dye difiuses into the dye transfer layer and is firmly fixed there.
  • This process is identical with the color photographic process according to dye transfer which is called an imbibition or dye transfer process.
  • an inorganic colloidal precipitate such as aluminum hydroxide or magnesium hydroxide was used before.
  • mordanting agents are cationic polymers comprising the abovementioned nitrogen-containing organic compounds.
  • mordanting agents are poly-2- vinylpyridine (I), poly-4-vinylpyridine or a quaternary salt thereof (ll), many polymers of chain or cyclic ammonium salts (III to X), and aminoguanides of vinyl polymers or starch oxides (XI to Xlll). Structural formulas of typical mordanting agents are as shown below.
  • the above-mentioned cationic polymer may be incorporated as it is into such a dye transfer layerforming hydrophilic colloidal binder as gelatin, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, starch or a derivative thereof.
  • the said polymer may be incorporated as a fine coaservate, which is formed by reacting the polymer in an aqueous medium with gelatin, polyvinyl alcohol or a phthalic derivative of starch.
  • the amount of the polymer is about 0.] to 1.0 g. per in of the finished dye transfer layer.
  • a photosensitive material is prepared by coating on a support one or more silver halide layers containing a coupler capable of splitting off the aforesaid anionic dye. After proper exposure, the thus prepared photosensitive material is superposed face to face on a dye transfer sheet having a dye transfer layer which has sufficiently been coated with a viscous developer. Alternatively, the two sheets are individually dipped in a developer for about seconds so as to sufficiently absorb the developer, and then the photosensitive material is superposed face to face on the dye transfer sheet.
  • the resulting photographic mate rial When the resulting photographic mate rial is allowed to stand after slight squeezing, exposed silver halide in the photosensitive material is developed and, at the same time, an anionic dye, which is formed by the aforesaid coupling reaction, diffuses from the photosensitive emulsion layer to the dye transfer layer.
  • the anionic dye In this dye transfer layer, the anionic dye is captured by a cationic polymer, which is the mordanting agent, to form a complex, with the result that the anionic dye is deprived of its diffusibility and is fixed. Accordingly, when the photosensitive material is peeled off from the dye transfer sheet, a desired color photographic image is obtained in the dye transfer layer.
  • a accelerator such as a cationic onium salt as, for example, tetrabutylammonium bromide or N-(B-phenethyll-methylpyridinium p-toluenesulfonate.
  • a cationic onium salt as, for example, tetrabutylammonium bromide or N-(B-phenethyll-methylpyridinium p-toluenesulfonate.
  • the developing agent used is a paminoaniline derivative, which does not undergo the influence of potential barrier of silver halide particles. Accordingly. the accelerator is entirely ineffective, or rather inhibits the development. in some cases, though this is a matter of course.
  • B-phenylethylamine which is well known as an accelerator for the ordinary color development. is also low in effectiveness in the color development dye transfer process according to the present invention in which a diffusing anionic dye is separated, and shows an apparent sensitivity increase of only 0.1 to 0.2 in terms ofa logarithmic value.
  • various alkyl-, arylor aralkyl-amines which are said to be effective in the ordinary color development. are also ineffective or inhibitory. and no accelerator capable of ef fectively accelerating the development dye transfer has not been discovered yet. However, it has been found that diaminoethane, diaminopropane.
  • diaminobutane, diaminohexane, diaminoheptane. diaminooctane, diaminononane, diaminodecane, diaminododecane and the like diaminoalkanes and polymethylenediamines can greatly accelerate the development dye transfer. in general, unlike the monoamines. It has also been found that diethylenetriamine. triethylene' tetraethylenepentamine. dipropylenetria mine. tripropylenetetramine. tetrapropylenepentamine and dipropylenebutylenetetramine (another name: spermine) formed by connecting the molecules of said ethylenediamine. propylenediamine, butylenediamine, etc. are also effective.
  • the former accelerators are mostly those which cor respond to the formula NH (CH ),,-NH
  • diaminopropanes corresponding to the above-mentioned formula as, for example, 1,3 diaminopropane (NH -CH -CH -CH --NH and l,2diaminopropane (Nik -Eli sll lfi i l
  • the former accelerators can be represented by the formula which may be abbreviated to
  • the latter accelerators have such structural formulas as shown below which are arranged in the above-mentioned order.
  • R is a hydrogen atom or a lower alkyl group
  • n. p and q are positive integers, and it has also been found that the substances are practically effective when n is l to 9, p is 2 to 4 and q is l to 4.
  • the effective substances have collectively been defined. The relation between the number of carbon chains and the effectiveness will be mentioned in detail later. Further, alcohols themselves have no accelerating effects at all and are rather inhibitory, but can greatly increase the effects when used in combination with the aforesaid substances and hence are extremely useful, as will be mentioned later. There might be some other substances which are similar in supplemental effects to those mentioned above. In the present invention, however, the accelerators have been limited to substances which are substantially effective.
  • the aforesaid polymethylenepolyamine as a sensitizer for silver halide emulsion is added in such a slight amount as 5 to 50 mg. per mole of silver halide which is 170 g. in terms of AgNO (refer to US. Pat. Nos. 2,518,698 and 2,743,182).
  • the amount of silver halide coated thereon is about 1 to 10 g/m in terms of AgNO
  • the amount of the above-mentioned sensitizer is as minute as 0.03 to 0.3 mg/m 0.00003 to 0.0003 g/m).
  • the development dye transfer accelerating mechanism of the aforesaid substances has not been elucidated yet, but is not a mere phenomenon of accelerating the color development, as is clear from the abovementioned fact that substances, which have been effective hitherto, are ineffective or scarcely effective.
  • the present inventors consider that the said substance complexes with an anionic dye (the amino group forms a salt together with the anion group) to take such a form as to be easily movable in gelatin or the like colloidal binder in an aqueous medium less in ionic property, and the substance acts as a carrier for the dye molecules to bring the dye quickly from the circumference of silver halide, in which the dye has been formed, to the dye transfer layer, with the result that the color development itself is accelerated.
  • an anionic dye the amino group forms a salt together with the anion group
  • the substance, which is effective in the above case. includes not only l,8-diaminooctane and l,6-diaminohexane which are difficulty soluble in alcohol or water but also 1,2- diaminoethane and 1,3-diaminopropane which are more easily soluble in water rather than in alcohol. it may be said that the development dye transfer accelerator mechanism of such substances cannot be explained at present, unless the above-mentioned hypoth esis of carrier is adopted.
  • the present inventors investigated low molecular weight guanidines which have a property of forming complexes together with anionic dyes, like the polyamines. As the result, the inventors have found that the guanidines are markedly different from the polyamines, since they are ineffective or tend to inhibit the development, like the aforesaid cyclic monoamines, pyridine, cyclohexylamine and piperazine. Considering the fact that when used in dyeing, both the polyamines and the guanidines act as fixing agents for anionic dyes, it is understood that the development accelerating effects of said substances cannot be easily inferred and that the actions of the polymethylenepolyamines used in the present invention are quite unique.
  • FIG. 1 is a graph showing the relation between concentrations and apparent sensitivity increase values (AS) of l,n-diaminoalkanes in processing solutions.
  • FIG. 2 is a graph showing the relation between carbon chain numbers (n) of l, n-diaminoalkanes [NH (CH ),,NH ]and limiting effective concentr tions thereof in the case where alcohol is not added to the developer (H O system) and in the case where alcohol is added to the developer (10 EtOH system) which are obtained from FIG. I, in addition to the relation between corresponding carbon chain numbers and limiting effective concentrations of other polymethylenepolyamines.
  • FIG. 3 is a graph showing the variation in characteris tic curves of magenta dye due to prolongation of the development dye transfer time in the case where the developer used has not been incorporated with acceler ator, in comparison with the variation in characteristic curves of magenta dye in the case where the development dye transfer is effected for 2 minutes in the presence of varying amounts of 1,6-diaminohexane as accelerator.
  • the effect of accelerator in the case where the amount of accelerator is increased in identical with or more than that in the case where the time is prolonged whereas as to the maximum density, the former effect does not always compensate the latter effect.
  • the effect of accelerator in the above case is quite satisfactory because in the case of a color print having three color layers, it is sufficient that the maximum reflective density of one color is l.2 (the maximum reflective density of black color formed from the three colors becomes 2.5 or more).
  • the apparent sensitivity increase is not the actual sensitivity increase, because the accelertor is not present at or before the time of exposure but is added to the system at the stage of development dye transfer, and is used for the reason that the characteristic curve moves to the left like in the case where the development time is prolonged or the liquid temperature is increased.
  • the amount of characteristic curve, which has moved to the left in parallel to the axis of log E (logarithm of exposure amount) of the characteristic curve at a definite density e.g. a reflective density of 0.5 to 0.8
  • AS apparent sensitivity increase
  • the amount of accelerator and the effect thereof it is also important to contrast the amount of accelerator and the effect thereof. It is desirable to use a accelerator which is effective even when used in a small amount, but there is an accelerator which, despite of its being effective even when used in a small amount, is not increased in effect even if the amount thereof is increased. Further, when the amount of accelerator is increased, the amount of fog is also increased, in general. However, there is also an accelerator which makes the amount of fog greater before the effect thereof has not sufficiently been displayed, or an accelerator which is increased in effect but do not increase the amount of fog. Thus, the relation between the effect of accelerator and the amount of fog formed should also be taken into consideration. Furthermore, the effect of accelerator is greatly affected by the conditions adopted, i.e.
  • the five lines at the lower part of FIG. 1 show the cases where the substances of the above-mentioned formula. in which n is 2, 3, 4, 6 and 8, are individually added to a developer containing no alcohol. From the said lines, it is understood that the limiting effective concentration markedly decreases with increasing carbon chain. That is, the compound C is effective even when used in l/lO the amount of the compound C but tends to be rather lowered in AS value, which is the absolute value of effect.
  • the five lines at the upper left portion of FIG. 1 show the cases where a part of the solvent of the development dye transfer processing solution has been substituted with an alcohol l ethanol solution).
  • An accelerator having or more carbon chains is scarcely soluble in water, and therefore the alcohol should necessarily be added.
  • the alcohol is added, the said compound is markedly increases in accelerating ability, regardless of the number of carbon chains, with the result that not only the limiting effective concentration decreases from 1/5 to l/ but also the value of apparent sensitivity increase (AS) itself increases to a great extent.
  • AS apparent sensitivity increase
  • the accelerator may be used, as being compensated with the molecular weight thereof, in such a proportion as 0.15 to 3.0 g/liter, Le. a molar concentration within the range of 1:20, which is somewhat narrower than the range of l:50.
  • the accelerator when used in large amounts, tend to act as foggants for silver halide emulsions. Accordingly, it is impossible to introduce them directly into photosensitive emulsion layers,
  • the accelerator can be freely incorporated into the mordanting agent-containing colloidal binder layer of a dye transfer material or into a layer adjacent thereto.
  • this procedure is adopted, there is brought about such advantage that a suitable amount of the accelerator can be accurately fed during the development dye transfer treatment without adding the accelerator to the development dye transfer processing solution. Further, there are such effects that not only can the processing solution be prepared easily and conveniently but also it can be stored for longer periods of time.
  • the processing solution is ordinarily disposed between the photosensitive material and the dye transfer material of a photographic material which have been individually coated on separate supports as set forth in Example 1 shown later and which have been contacted face to face with each other.
  • the amount of the processing solution varies depending on the extent of squeezing of the photographic material and the liquid absorption properties of the photosensitive material and the dye transfer material, and hence is not definite. However, generally from 100 to 200 ml/m of the processing solution is present between the two during the treatment.
  • the accelerator in the above case requires a longer dissolving-out time than in the case where it is added to the developer, and does not reach an equilibrium concentration in a short period of time, so that the accelerator should have been added in excess as much. That is, the accelerator is required to be added in a considerably larger amount than 0.0l5 to 0.60 g/m which is a value obtained by simply calculating the amount of the accelerator in the above-mentioned processing solution into the amount thereof per unit area.
  • the amount of each accelerator varies depending on the thicknesses of water absorption layers of photosensitive material and dye transfer material, the treatment procedure and the treatment time, but is required to be 2 to 3 times the above-mentioned value, and may collectively be 0.03 to 2.0 glm It is, of course, possible to transfer not only the accelerator but also the color developing agent and other components in the developer into the mordanting agent-containing colloidal binder layer or into a layer adjacent thereto.
  • EXAMPLE 1 In this example is illustrated a photographic material comprising a photosensitive material and a dye transfer material which have individually been coated on separate supports.
  • the photosensitive material was prepared in the following manner.
  • the emulsion was then incorporated with a small amount of a lN-NaOH solution to make the pH thereof 6.3 as well as to make the total amount thereof 500 g. Thereafter, the emulsion was coated on a baryta paper of 190 g/m so that the amount thereof became 80 glm On the resulting emulsion layer was further coated 50 g/m of a 3 percent gelatin solution as a protective layer, which was then dried to prepare the photosensitive material.
  • the dye transfer material was prepared in the following manner.
  • the photosensitive material was subjected to stepwise exposure through an optical wedge, and then dipped for 20 seconds (at 20C.) in a dark chamber in an activator solution formed by removing the developing agent from the standard color developer of the prescription shown in the table below.
  • the dye transfer material was dipped for 30 seconds (at 20C.) in the color developer so as to sufficiently absorb the developer. Thereafter, the two materials were contacted face to face with each other. The resulting photographic material was carefully squeezed so that no air was interposed between the two materials.
  • the development dye transfer time was limited to 2 minutes, and the photographic material was treated with each of 4 developers prepared by adding each 0.5, 1.0, 2.0 and 4.0 ml/liter of 1,6-diaminohexane to the color developer.
  • the accelerator was not favorable in water solubility, so that l0 percent of water in the developer was replaced by ethanol. Accordingly, the above-mentioned curves ought to be compared with the curve of the blank sample represented by the dotted line.
  • the maximum density is considerably low, as mentioned previously.
  • the density is a reflective density, so that the accelerator according to the present invention is favorably used for the development of monochromatic photographic material and is used sufficiently satisfactory for the development of color photographic material having three colored layers.
  • Example i was repeated, except that the accelerator was replaced by each of l,2-diaminoethane (represented by C following the number of carbons; the same shall apply hereinafter), 1,3-diaminopropane (C 1,4-diaminobutane (C l,6 diaminohexane (C this overlaps the accelerator used in Example I), l,8- diaminooctane. and LlO-diaminodecane.
  • the results obtained were represented only by the values of apparent sensitivity increase (AS) and, for comparison, the concentration of the additives were represented by molar concentrations (mM), as shown in FIG. 1. From FIG.
  • the accelerating effects do not increase in proportion to the number of carbon atoms.
  • the numbers of carbon chains between NH; and NH, as measured by considering that NH is also identical with CH are 2, and 8, as shown below.
  • the corresponding carbon number is 3.5.
  • the limiting effective concentration thereof is above the straight line when no alcohol has been added, and is below the straight line when alcohol has been added. This is considered ascribable to the point that in the aqueous system, 2Pr3A displays an action similar to that of a polyamine small in number of carbon chains, while in the alcohol-incorporated system, it displays an action similar to that of a polyamine large in number of carbon chains. This not only shows that the above-mentioned idea of corresponding car bon chains is substantially correct, but also clarifies the relation between the effects of said polymethylenepolyamines as accelerator and the molecular structures thereof.
  • EXAMPLE 4 The same commercially available RC paper as in Example l was subcoated with about 80 g/m of a solution of the composition shown below to form a neutralization layer.
  • Vinyl methyl ether-maleic anhydride copolymer (Commercially available PVM/MA produced by Mitsubishi Chemical Co.) 5 Polyvinyl alcohol l0 Gelatin l2 Ascorbic acid 0 Water (neutralized with alkali to pH 4.0) to make the total amount
  • l2 g. of the aforesaid cationic high polymer mordanting agent of the structural formula (V) was dissolved in 240 ml. of water, and the resulting solution was heated to 50C. This solution was poured in the form of a fine stream with stirring into a solution kept at 250C, which had been formed by dissolving 24 g.
  • the thus formed colloidal binder solution was coated on the neutralization layer, which had been formed on the aforesaid RC paper, and then dried to prepare a dye transfer material.
  • This dye transfer material was contacted face to face with the same photosensitive material as in Example I to prepare a photographic material.
  • the thus prepared photographic material was subjected to development dye transfer for 2 minutes using the activator-incorporated standard color developer used in Example 1 to obtain a standard sample (a).
  • the photographic material was treated with the standard developer incorporated with 5.0 g. of sodium thiosulfate (pentahydrate) per liter of the developer to obtain a sample (b); with the standard developer incorporated with 5.0 g.
  • EXAMPLE 5 EXAMPLE 6 5 grams of the aforesaid cationic high polymer mordanting agent poly-(4-vinylpyridine)toluenesulfonate having the structural formula (Ii) and I g. of polyvinyl alcohol were dissolved in 501) ml. of water. To the resulting solution was added a solution of g. of 1,8- diaminooctane in 100 ml. of ethanol. The mixed solution was coated by use of an extrusion coater on a transparent triacetate film base in such an amount as to form a film having a dry thickness of about 3;; (i.e. 120
  • a solution (total amount 500 g.) containing g. of a polyvinyl pyrrolidone (PVP K-QO produced by GAF Co. of the United States), 25 g. of a percent polyacrylamide solution ("Kogam 20" produced by Kobunshi Kagaku K. R. t, l g. of a decolorizing dye (purplish brown color) and 5 g. of saponin was coated by use of an extrusion coater in such an amount as to form a film having a dry thickness of about 1.2a (i.e. 30 g/m).
  • an extrusion coater On the resulting film were precisely coated by use of an extrusion coater (1) a redsensitized silver chlorobromide emulsion incorporated with a non-diffusible yellow coupler splitting off diffusion cyan dye of the formula,
  • l T can in which emulsion, 50 percent of the gelatin to be used had been replaced by carboxymethyl cellulose; and (6) as an over layer. a liquid of the same composition as in (2), in this order. followed by drying, to form a photosensitive material portion. in this photosensitive material portion.
  • the composition and silver content of the emulsion, the amounts of the couplers used, the thickness of the individual films, etc. were identical with those in the case of a commercially available color paper, unless otherwise specified.
  • the finished photographic material obtained in the above manner is used for the printing of cinefilms, in general. but may be used for the printing of color slides and large sized transparent color photographs. That is, the photographic material is printed from a color negative. exposed to light, developed for 2 minutes in a vat,
  • Example 1 like in the case of ordinary photographic material, with the developer used in Example 1 which had been freed from the 1,6-diaminohexane, and then washed with water, whereby the photosensitive material portion is washed off and only the dye transfer layer bearing a color positive image remains on h r 'is rent film base, so that it is sufficient to dry the dye transfer layer.
  • the processing can be effected quickly, and the result can be observed mmediately.
  • the accelerator incorporated into the dye transfer layer not only diffuses in the photosensitive emulsion layer but also diffuses and dissolves in the developer, and when a cinefilm or the like long film is developed according to the above-mentioned development process, the accelerator accumlates in the developing bath. in order to obtain a definite result, therefore, the developing bath should have been incorporated with the accelerator, even when a suitable amount of the accelerator has already been added to the dye transfer layer. Moreover, the developing bath should always be strictly managed and renewed as it is fatigued. Thus, the above-mentioned development process is difficult for amateurs. It is therefore preferable to adopt such a process as mentioned below.
  • a development belt is separately prepared by thickly coating (to a dry thickness of about 2514) a 15 percent gelatin solution on a base (preferably an RC-base), which is substantially identical in elongation with the film base used, followed by drying.
  • the thus prepared belt is dipped in the aforesaid developer (containing 10 percent ethanol but no accelerator) to sufficiently absorb the developer.
  • the belt is super posed face to face with the aforesaid exposed film and then rolled up with care so that no air bubbles are disposed between the two, and the rolled film is allowed to stand at normal temperature for at least 2 minutes.
  • the developer used for the development is always fresh, and a proper amount of the accelerator is supplied from the dye transfer layer.
  • the developer is used in a definite amount per definite area, so that the development is not substantially affected by time and temperature. Accordingly, the abovementioned process is not only easy for amateurs to obtain a definite result, but also advantageous for those skilled in the art.
  • the rolled film is unrolled and then washed with water, whereby the photosensitive emulsion layer disperses and flows out in the water, so that the film can be projected immediately after drying. Since a suitable amount of the mordanting agent has been incorporated into the dye transfer material portion, the dye transfer can be effected quickly and a color positive image less in fog and definite in color tone and density can be obtained.
  • EXAMPLE 7 A color film was prepared in the same manner as in Example 1. except that a high sensitivity silver iodobromide emulsion was used in place of the silver chlorobromide emulsion, and 50 percent of the gelatin in the photosensitive material portion had been replaced by carboxymethyl cellulose like in Example 6.
  • This color film is particularly useful as an amateur cinefilm. That is, after photographing, the film is superposed face to face with the development belt of Example 6 which has absorbed a black-white developer, subjected to first development at 30C. for 7 minutes, peeled off from the belt, and then washed with 3 percent magnesium sulfate.
  • both sides of the film are subjected to second exposure (for a total of 2 minutes) by irradiation with a 500 W lamp positioned at a distance of 30 cm.
  • the film is again dipped in the same developer as in Example 1, except that 2.0 ml/liter of 1,4-diaminobutane has been used in place of the 1,6-diaminohexane to absorb the developer into the film, treated at 30C. for 3 minutes, and then washed with water to remove unnecessary photosensitive emulsion layer, whereby a color positive image high in gradation and density is left on the base. Accordingly, the film can be projected immediately after drying.
  • EXAMPLE 8 The same dye transfer layer as in Example 6 was coated, in the same manner as in Example 6, to a thickness of about 3pm on a polyester base to prepare a dye transfer material (in which 6 g. of l,6-diaminohexane had been contained as an accelerator in place of g. of the l ,S-diaminooctane).
  • the photosensitive material was subjected to direct photographing, or to electronic recording or contact printing from other microfilm, and then dipped for 1 minute in the activator used in Example 1 to sufficiently absorb the activator. Immediately thereafter, the photosensitive material was closely contacted face to face with the dye transfer material, allowed to stand for 2 minutes and then peeled off, whereby a magenta colored micro image was obtained on the surface of the dye transfer material.
  • an image obtained in a similar manner as above ought to be somewhat low in resolution, due to the diffusion of dye at the stage of dye transfer.
  • the image obtained in this example was unexpectedly good in resolution due to the facts that the dye transfer material had contacted with the most sharp image on the surface of the photosensitive material, the film was thin, and the granularity of color image ascribable to the silver halide particles had substantially been disappeared.
  • the thus obtained image was a colored image, and hence had such characteristics that it was free from the drawback of white dot, which frequently comes into question during the storage in a dark place ofa silver image-bearing microfilm (i.e. the partial bleaching of silver image due to peroxides derived from containers and the like), and was higher in absorbancy index than a silver image.
  • the color is not limited to a magenta color, but may be a mixture of yellow and cyan colors.
  • the coupler is incorporated so as to be in conform to the spectral wave length characteristics of scanning light source used at the time of reproduction thereof.
  • a color development dye transfer method in which a color photograph is obtained quickly by using a dye transfer color photographic material comprising a portion composed mainly of a photosensitive silver halide emulsion layer containing a non-diffusible coupler capable of splitting off a diffusible anionic dye by coupling, in combination with a portion composed mainly of a dye transfer layer containing a cationic higher polymer mordanting agent layer capable of fixing therein the diffused anionic dye, subjecting the photographic material to exposure and color development to fix in the dye transfer layer the anionic dye splitted off by the coupling reaction, and then removing the unnecessary photosensitive emulsion layer portion therein by leaving the dye transfer layer in which a desired color image is formed, the improvement which comprises accelerating the dye transfer rate of color development by affecting dye transfer in the presence of a mixture of an alcohol and at least one of polymethylenepolyamine derivative having the general formula,
  • R is a hydrogen atom or a lower alkyl group
  • n, p and q are individually a positive integer of from 1 to 9, 2 to 4, and l to 4, respectively without directly introducing said polymethylenepolyamine derivative directly into said silver halide emulsion layer.
  • a dye transfer color photographic material for use in the color development dye transfer photographic method described in claim 1 which has such a structure that a dye transfer layer portion and a photosensitive silver halide emulsion layer portion have been coated on one support together with auxiliary layers so that before the exposure and development dye transfer treatment, the two portions are in a unified state and, after the development dye transfer treatment, the photosen' sitive emulsion layer portion is removed, if necessary together with the auxiliary layers, in which said mate rial comprises as a set, a photosensitive silver halide emulsion layer, a non-diffusible coupler capable of splitting off a diffusible anionic dye by coupling with a developing agent and a mordant layer containing a cationic high polymer between which an inter hydrophilic colloide layer is interposed, characterized in that at least one of the polymethylenepolyamine derivatives set forth in claim 1 has been incorporated in a total of 0.03 to 2 g. per m of the photographic material into a layer other than

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JP452872A JPS556214B2 (enrdf_load_stackoverflow) 1972-01-07 1972-01-07

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US320822A Expired - Lifetime US3887370A (en) 1972-01-07 1973-01-03 Dye transfer acceleration with polyamine compounds

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US (1) US3887370A (enrdf_load_stackoverflow)
JP (1) JPS556214B2 (enrdf_load_stackoverflow)
DE (1) DE2300772C3 (enrdf_load_stackoverflow)

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EP0617326A3 (en) * 1993-03-18 1996-05-29 Fuji Photo Film Co Ltd Color diffusion transfer photosensitive material.

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JPS5529418B2 (enrdf_load_stackoverflow) * 1973-10-24 1980-08-04
JPS5530217B2 (enrdf_load_stackoverflow) * 1974-04-19 1980-08-09
JPS5574541A (en) * 1978-11-29 1980-06-05 Konishiroku Photo Ind Co Ltd Film unit for color diffusion transfer photography
JPS55101944A (en) * 1980-01-21 1980-08-04 Fuji Photo Film Co Ltd Color diffusion transfer method
JPS6034198U (ja) * 1983-08-12 1985-03-08 三菱重工業株式会社 低温液化ガス貯蔵槽

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US2191037A (en) * 1938-11-12 1940-02-20 Eastman Kodak Co Color forming developer containing amines
US2515147A (en) * 1947-08-26 1950-07-11 Gen Aniline & Film Corp Photographic developer containing an aralkylamine and process of development
US2518698A (en) * 1948-11-18 1950-08-15 Eastman Kodak Co Chemical sensitization of photographic emulsions
US2857275A (en) * 1954-11-08 1958-10-21 Polaroid Corp Photographic compositions and processes
US3173786A (en) * 1960-08-22 1965-03-16 Polaroid Corp Color diffusion transfer process, element and composition therefor
US3698896A (en) * 1970-12-21 1972-10-17 Eastman Kodak Co Diffusion transfer film unit with improved dye image receiving layer comprising a basic polymeric mordant
US3718464A (en) * 1971-08-24 1973-02-27 Eastman Kodak Co Development accelerators for image transfer systems

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US2191037A (en) * 1938-11-12 1940-02-20 Eastman Kodak Co Color forming developer containing amines
US2515147A (en) * 1947-08-26 1950-07-11 Gen Aniline & Film Corp Photographic developer containing an aralkylamine and process of development
US2518698A (en) * 1948-11-18 1950-08-15 Eastman Kodak Co Chemical sensitization of photographic emulsions
US2857275A (en) * 1954-11-08 1958-10-21 Polaroid Corp Photographic compositions and processes
US3173786A (en) * 1960-08-22 1965-03-16 Polaroid Corp Color diffusion transfer process, element and composition therefor
US3698896A (en) * 1970-12-21 1972-10-17 Eastman Kodak Co Diffusion transfer film unit with improved dye image receiving layer comprising a basic polymeric mordant
US3718464A (en) * 1971-08-24 1973-02-27 Eastman Kodak Co Development accelerators for image transfer systems

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0617326A3 (en) * 1993-03-18 1996-05-29 Fuji Photo Film Co Ltd Color diffusion transfer photosensitive material.

Also Published As

Publication number Publication date
DE2300772B2 (de) 1974-10-17
JPS556214B2 (enrdf_load_stackoverflow) 1980-02-14
JPS4875030A (enrdf_load_stackoverflow) 1973-10-09
DE2300772A1 (de) 1973-07-12
DE2300772C3 (de) 1975-06-05

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