DE1547906A1 - Photographic developer - Google Patents

Description

Dr. Walter Beil Ma! 1956

EfeHans Joachim Wolff Dr. Hans Chr, hatchet

Frankfurt a. M. - Most

- T «L 3t M #

Our Fri, 12 711

General Aniline ft film Corporation 'Ho * toric, ΪΓ.Υ., V.St.A.

Photography by former developer

The invention relates to developers and in a special photograph! E.g. the effective sensitivity to light is thus more developed noticeably improve photographic materials

Photographic film materials currently commercially available at Sititn sum for the most part have the required accuracy and fine-grainedness to meet the normal requirements. Requirements of the MthrzaM. to satisfy consumers. How, however, began. i * t _f . The aenaitometric properties of a given photographically sensitized material are essentially determined by means of factors, the intensity of the exposure to which the material is exposed and the maximum density that can be achieved by developing the film, the latter in turn depending on the type and manner in which the movie is developed and the Ua door of the developer

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components contained in the liquid. If accordingly two Samples of the same film material are exposed equally, and a sample is treated with a black developer while the other sample is developed to an equal gamma with a very strong developer, it can generally be said that in the second case a higher photosensitivity of the film is obtained than in the first case.

The so-called strong developers available so far, ie those that give maximum density values with shorter development times, have in many cases only given a slight advantage over the less effective developer liquids. The presently known high-sensitivity developers have been able to significantly reduce development times, but in many cases they cause serious problems such as excessive fogging and graininess and general softening of the photographic films developed with them. The effect of the formation of silicones is, of course, an increase in the velvet diameter of the negative obtained and a decrease in the image contrast in the less exposed areas. As a general · rule ₉ that the · 9ohleierdiohte in highly sensitive film great is formed and at elevated Entwioklungeseit and / or temperature more pronounced · As a result, often occur beträohtliohe difficulty in achieving the proper gradation on "and" was prescribed in particular within the for developing Period.

In order to explain the above, it was assumed that the developing effect which takes place mainly appears to occur in the surface areas of the exposed layer, which is probably due to the penetration resistance of the gelatin film against the developer liquid.A lengthening of the development time to promote deeper penetration into the exposed layer, which would be the case with weak developer liquids, has also proven to be unsatisfactory, since this always results in a noticeable increase in the Fogging properties result. In addition, the use of weak developers

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required excessively long development times their economic applicability.

In an effort to overcome the foregoing and similar problems, the art has been making use of photographic developing fluids made with certain chemical compounds, i.e. accelerators, anti-soling agents, stabilizers, etc. For example, it has been suggested that the addition of polyethylene glycols as well as certain functional derivatives - these connections to aqueous developer liquids a v / j3-ntliehe shortening of the necessary for the development, Time span causes. As examples of other compounds which can be used for a similar purpose, i.e., as a development accelerator has been proposed, the guanazoles, certain water-soluble inorganic salts, various bispyridinium salts, Hydrazines and various substituted ureas and thioureas, water-soluble ammonium salts and the like called " will. Although they show some improvement, calibrated the connections of the aforementioned type nevertheless proved to be unsatisfactory in various void points. While they often achieve optimum density with shortened development times, Perhaps their main disadvantage is their inability, fogging and graininess to be acceptable To prevent mass. Furthermore, it has been found that such preconditions for effective application are relatively strict conditions require. For example, their concentration must be kept within fairly precise limits, since they are relatively insignificant Variations in their amounts often negate their overall effect, with the result that in some cases the effective one The sensitivity of the silver halide photographic layer is actually lowered.

In any case, it was found that none of the chemical accelerators available to date is able to exceed the sensitivity the optimum speed peculiar to photographic film or it is due to the nature of the developer used.

The advantage of the present invention lie _t -t that it comparable

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improved photographic developer provides the excellent Have sensitivity and fine grain characteristics.

The improved developer compositions of the present invention have little or no tendency to obscure the silver halide haloids that have developed with them. You are also through marked a marked reduction in development time when used for photographic processing.

The present invention is based on the fact that developer compositions for silver halide roofing can be synergistically modified advantageously by giving them a small amount of a water-soluble polyoxyalkylenated derivative of 1,4-butynediol is added.

The developer mixtures modified in this way make it possible to achieve effective film speeds which are substantially, ie up to 50 io and more, above the optimum speed which can normally be achieved with the silver halide layer in question and / or the developer used.

The 1,4-butynediol polyoxyalkylenated derivatives used according to the present invention are represented by the following structure formula

R, Rj

Hf-ORH-O-C SiSC-CO- [RO-IH

L 1 j I LJ _n

Type Aj

^Λ 4

shown, in which R is an ethylene or propylene radical R ,, Rp, R, and R. a hydrogen atom or a lower alkyl radical with 1 to 4 carbon atoms, which can be the same or different, i.e. independently a methyl, ethyl, propyl, isopropyl, butyl or isobutyl radical and in which m and η are positive integers mean whose Sumii.e has a minimum diameter of 7, so that the molecular weight of the accelerator is at least is around 400.

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- ⁵ "1547306

The alkylene oxide adducts corresponding to the above formula can! be produced by known methods.

For example, a certain 1,4-butynediol can with a or more alkylene oxides in the presence of a small amount. a catalyst, usually an alkaline catalyst such as sodium hydroxide, at atmospheric or superatmospheric Pressure can be implemented using elevated temperatures between, for example, about 100 ° and 200 ° «The reaction can in the presence of an inert solvent and up to the desired Dimensions to be carried out; usual cooling devices can be used to dissipate the heat of reaction.

The amount of alkylene oxide used in the reaction depends on the average molecular weight of the desired product. Once the products are obtained, the 1,4-diol is treated with the alkyl oxide until the peeler hydroxyl hydrogen according to the above formula contains at least one mole of ethyl oxide. The addition of de> a Alkyleno, «yde to jf-ηί, ΰ Bv t.-o ^ -., - ' : τ'ψρ & can be balanced or unbalanced a a, ie, jeü'j κ .. ^1:; ^ about the same or a vm terse hi adlioc · byHcVmiddling all of Qxyalkylengruppen per chain contain.

The molecular weight of the polyoxyalkylated 1,4-butynediols depends on the amount of ethylene used in the reaction and can easily be determined by analyzing the hydroxyl content. The hydroxyl steel is a measure of the hydroxyl concentration per unit weight and is proportional to it. The hydroxyl number is defined as milligrams of potassium hydroxide equiralent per gram of the 1,4-butynediol reaction product and is obtained by reacting acetic anhydride (in pyridiril solution) at reflux temperature with the hydroxyl groups of the alkylene oxide 1,4-butynediol reaction products. The unreacted anhydride and the acetic acid formed is titrated back with aqueous sodium hydroxide using phenol ph thai ei η as an indicator "Kaiin The molecular weight spawns aufgrunl the hydroxyl ζ ARUE r.aoh the f ο 1 ge η as η Fo r ω e 1 bere, r ·. η β ■, ns γ; I ¹ -. ·,:.:

BATH ORIGINAL

Functionality χ 1000 χ 56.1 Molecular Weight - Hydroxyl Number

The amount of water soluble used in the developer mix polyoxyalkylenated 1,4-butynediol is not particularly suitable decisive and can fluctuate within a wide range. ken. In this regard, it has been found that amounts as low as 0.25 g to to 30 g and more per liter of the developer mixture especially are suitable. Quantities significantly above the aforementioned value are usually not justified, since the improvement achieved is in many cases due to the increased caused thereby Costs would be recouped. It was found that the aforementioned compounds within the recommended concentration range, increases in sensitivity in the order of magnitude of 50 # and more than can be expected using the usual developer principles.

The polyoxyalkylenated butynediols intended for use according to the invention must meet a number of essential requirements, namely (1) they must be water-soluble and {2) contain a total of at least 7 combined alkylene oxide units. The issue of water solubility is of considerable importance in connection with compounds represented by the above formula in which one or more of the attached B groups is an alkyl group. As the number of carbon atoms is increased, the compound becomes correspondingly more hydrophobic, as can easily be seen. However, it has been found that, within the limits expressed by the above formula, the desired degree of water solubility, regardless of the hydrophobic character imparted by the attached alkyl substituents, is achieved when the number of alkylene glycol units is at least 7. For example, it has been found that compounds which we; Contain more than the prescribed minimum of bound alkylene oxide units, do not have the required solubility in aqueous developer solutions and for the formation of undesirable leanness n <± i _c ; en.

BATH ORIGINAL

Optimum results are expressed as a percentage obtained with compounds in which the alkylene oxide units account for at least 60 i °, and preferably 75 to 95 $ of the Butindiolderivata. The amount of combined alkylene oxide units can exceed the aforementioned maximum, since all derivatives within this range have the required solubility in developer mixtures for silver halides. In terms of molecular weight, the polyoxyalkylated 1,4-butynediols contemplated for use in the present invention fall in the range between about 400 and about several thousand, ie 4i on the order of up to 10,000-11,000. However, particularly favorable * results will be obtained obtained with derivatives whose molecular weights are within the range from about 900 to about 5000. Thus, the sum of m and η in the above formula can have an average value between about 7 and about 250, with a range between about 15 and about 100 being preferred. The higher molecular substances are obtained in the form of waxy, amorphous pesticides. However, there are no difficulties associated with the production of aqueous solutions, since the combined alkylene oxide units are sufficient to provide the necessary waste solubility.

The improvements achieved by the present invention are particularly evident when using potyoxyethylene derivatives of l ^ -dimethyl-l ^ -diisobutyl-l ^ rbutynediol. These adducts are given by the following formula

CH, CH

CH ₃ - ÜH - CH ₂ CH ₂ - CH - CH

_{3 2 2}

HT OCH ₂ ChXo - C - U == E CCO -T

UH ₃ CH ₃

uH ₂ CH ₂ O

shown, in the * 1: 1 and η the meaning given above to have.

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The compounds corresponding to the above formula are commercially available from Air Reduction Chemical and Carbide Company, a group of Air Reduction Company, under the trade name "Surfynol". These products are identified by a numerical code indicating the percentage of ethylene oxide units combined; for example, be referred to as "Surfynol 485" and "Surfynol 495" compounds of the above formula "that contain 85 or $ 95 i ° combined ethylene oxide.

Without being bound by any particular theory as to the effect of the above compounds in the development process to be, it was suggested that an adsorption of the polyoxyalkylenated Butynediol material on the silver halide grains takes place whereby micelles form. During the initial stages of development, the undissociated molecules of the Developer likely due to the effects of lipophilic Solubilized groups of micelles. During the course of the development reaction and while the concentration of the developer decreases, the effects of lipophilic properties Groups of the adsorbed micelles are supplied with fresh developer, whereby more developer is made soluble.

However, many of those previously used have been found to be Development accelerators and especially those with the desired softening and quenching effect, incidentally, do not contain gelatin adversely affect. In many cases, such compounds impair the physical properties of gelatine, e.g. by lowering the melting point and hardening point of the gelatine. In contrast, there is only little or no swelling effect in the case of the invention Connections and after removal of the firn from the developer liquid and soaking, the original physical properties of the gelatin are substantially restored. In addition, the excellent water solubility of the butynediol derivatives according to the invention provides a thorough and uniform distribution of the same in the layer which of course in the case of a multilayer color film to achieve balanced color values is of particular importance. ·

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The improvements achieved according to the invention range from any particular grade of silver halide developer ab * Therefore a hydroquinone developer can be used, i.e. a developer that contains hydroquinone, potassium metabi aulfite and potassium bromide contains or a metol-hydroehinone developer, i.e. a "Developer that p-methylaminophenol, Sodium sulfite, sodium bisulfite, Contains hydroquinone, sodium carbonate and potassium bromide. However, the developer mix can also be a so-called Borax developer aein, i.e. it can p-methylaminophenol, JTatriumsul fit, hydroquinone, borax and potassium bromide included. In a nutshell, the improvements provided by the invention will apply to virtually all types of exposed silver halide films easily achieved,.

The inventive. 1,4-buti ndiöl-poly oxy alkyl ened derivatives are extremely useful and give particularly favorable results when they are black-and-white development. misclien intended for use in conjunction with the ^^ reversal process of parbphotography. As is known, the latter method comprises the formation of Parbomponent CompletePja in each of a plurality of superimposed liquid-sensitive silver halide layers, each of which contain a non-diffusing color former, by a first development; an exposed silver halide, through which only the silver images are formed, and a subsequent renewed exposure and a second development for the formation of silver images and color images in situ in the reversing image areas of the Ulmschiohten. Not only is there an increase in the effective uniqueness of each of the color images formed for the sensitized layers in the range of 50 $ and more, but it has also been found that other advantageous results are also found. improved brilliance, color saturation and color density are obtained between the various layers; =

The following illustrations serve to explain the present Invention. '· ■ ·; -

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example 1

An amateur film, with a gelatin-silver halide layer containing 21 ° silver iodide and 98 % silver bromide, was exposed to form an image and treated for 5 minutes with a developer solution of the following formula:

Metol 1.5 g

Sodium sulfite, anhydrous 45 g

ftatriuinbi sulfite. Ig-

Hydroquinone 3g

Sodium carbonate (monohydrate) '6g

Potassium bromide 0.8 g

Water to make up to 1 liter

The developed film was then fixed and in the usual manner watered,

A second sample of the same film was made in the same manner exposed. "The exposed film was for 5 minutes with the above Treated developer solution, which is further polyoxyalkylenated with 4 com 1,4-Dimethyl- <1,4-dlisobutyl-1,4-butynediol was added containing 75 # combined ethylene oxide units. the obtained in the case of the usual, i.e. unmodified, developer relative sensitivity was 100, while the sensitivity that with the developer containing the butynediol derivative was achieved was 150. In addition, brought the increase sensitivity, no significant changes in clarity, gamma, or D-max.

The following examples illustrate the improved results obtained when using the polyoxyalkylenated 1.4 "" butynediol a Schwarzwais. ^ - developer is added, which in the reversal process color photography is used.

Example 2

A multilayered photographic film, the three superimposed (jelatine silver halide layers possessed, each

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sensitized in the blue, green or * red spectral ranges are, and each contain a non-diffusing color former for yellow, purple and cyan colored, whereby the blue sensitized layer on the outside became one Image exposed and 9 minutes in a standard black-and-white developer the following composition developed "

Metol. 1.5 g. ■■, ■ "■ ·

Sodium sulfite anhydrous 45 g

fjatriulibisulfite 1 g.

Hydroquinone - 3 g

jviatrium carbonate, (monohydrate) 6 g ^v

Potassium bromide 0.8 g

Water to make up to 1 liter

The film was then immersed in a 30 percent aqueous solution for 3 minutes Potassium cliromalum solution hardened, soaked for 3 minutes and for 1 minute, at a distance of 12 inches (30.48 cm) with a "photoflood" lamp No. 2 reverse exposure.

The film exposed in this way was then used for 10 minutes a common color developing solution having the following composition immersed:

Sodium hexametaphosphate 1 Sodium bisulfite 1

p-Aminodietliylanilln HCl 3

Natiiumcarbanate (monohydrate) 60

Hydroxylamine HCl. 1

Potassium bromide - 1.5

Water to make up to 1 liter

The developed film was placed in a break bath of the following composition for 3 minutes:

Cate trium acetate 20 g

Acetic acid 10 g

Water made up to 1 liter

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BAD ÖftlölNÄL

The EiIm treated in the lint erb reohungsb ad was in a 3 percent Potassium chrome alum solution hardened for 5 minutes.

After soaking in running water for 5 minutes, the film became ' treated in a bleach bath of the following composition:

Dipotassium monosodium ferricyanide 60 g

Potassium bromide 15 g

Disodium phosphate 15 g

T Sodium bisulfate 6 g

Water to make up to 1 liter

The developed material was soaked in water for 5 minutes and then fixed for 3 minutes in a solution of the following composition:

Hypo 200 g

± sorax 10 g

Water to fill up to x uiter

After fixing, the film was immersed in running water for 10 minutes watered j then left to dry.

A similar film treated in the same way, with however 5 ecm of the ρ ο Iy ο xy ä thy 1 entered 1,4-butynediols of the example Whenever black-and-white developers were added and that Developing lasted only 3 minutes at the same [temperature was compared with the film, "that with the unmodified one Black and white decoder had been dealt with. The color densities obtained in each of the three sensitized layers were respectively measured with red, green or blue light «The results obtained showed that the treatment with the modified Black and white developer an effective one in every aspect Film speed was found to be at least 0.30 log E greater was than the sensitivity that when using the unmodified Black and white developer was achieved.

• Example 3

Example 2 was again Joolt with the difference that the amount

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that contained in the modified black and white developer polyoxyethylene 1,4-butynediol was increased to 10 ecm * The reverse "image obtained in the three sensitized layers each was measured and it was found that the effective increase in sensitivity in each of the layers was at least 0.45 log E greater than that of the film sample obtained with the modified black-and-white developer had been treated.

In each of the above examples, the improvement was noted film speed without any adverse side effects in terms of fogging properties and / or the photographic quality of the image obtained, i.e. Clarity, contrast and the like achieved. "KLe results of the example 2 are particularly indicative. As indicated therein, there was a marked improvement in eye sensitivity in the case of the modified Söiiwarzweiss-Entwieklers achieved, as is shown by the results of the density measurements, despite the Fact that the development time is only a third of the development time cheat that in the case of the unmodified black and white developer solution was required.

As is clear from this, the use of development methods modified according to the invention photographic films to a hitherto unattainable extent, the commercial importance of such a process dated economic standpoint alone would be considerable.

Except for those specifically explained, are also used when using other polyoxyalkylenated 1,4-butynediols achieved results similar to those described in the examples above. As examples of such other compounds, especially the polyoxyethylene and polyoxyethylene Derivatives of the following compounds can be mentioned i

1 ^ 4-butynediol,

1,1,4,4-tetramethyl-1,4-butynediol,
l-methyl-4-ethyl-1,4-butynediol,
l, l-Diisopropyl-3-ethyl-l, 4-butiii-iiol, etc.

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Also will receive a similar improvement in Filmenipfindlichkeit if the above examples are repeated, but the special polyoxyäthylenierten diols include the following percentages combined Äthylenoxyds: 60 fo 70%, 85% i 90 $> or 95 $>. However, when the ethylene oxide content is reduced to a value well below $ 60, for example $ 50 to $ 55 or less, the polyoxyethylene derivative in question has a marked tendency to deposit like oil and form a sludge-like deposit on the photographic film materials treated therewith.

This problem increases as the molecular weight the 1,4-butynediol component is increased, i.e. when the Degree of alkylation is increased. Accordingly, within the The limits indicated above have found that the improvements achieved by the invention are maximized when considering the percentage of combined alkylene oxide units is increased to the extent that the molecular weight the butynediol component is increased. So was in the case of 1,4-butynediol itself, i.e. the unsubstituted compound, found that optimum results are obtained with polyoxyalkylenated derivatives of this compound in which the total number of combined alkylene oxide units have an average value within the lower part of the protruding! specified range, e.g. between 7 and 12. Conversely, in the case of higher alkylated butynediol derivatives, e.g. of polyoxyalkylenated 1,4-Dimethyl-1,4-diisobutyl-1,4-butynediol is particularly favorable Results achieved with alkylene oxide contents that have an average have a value of at least about 15 and up to 30 and more. In addition, it is on the pand that the polyoxyalkylenated 1,4-butynediol derivatives can be used effectively in the form of their mixtures, i.e. in the form of two or more derivatives which differ in Contains percentages of combined alkylene oxides. Furthermore, the improvements according to the invention are also achieved by using compounds made by implementation a 1,4-diol compound with mixtures of ethylene oxide and propylene oxide * Accordingly, such materials are considered to be equivalent »to those described in more detail above Viewing materials.

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It is obvious that those in the previous examples Introducing instructed specific developer by others developers described in more detail can be replaced. All common silver halide agents are suitable for use and this feature is in no way indicative of this critical in practicing the present invention.

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Claims (2)

PATE H TA Ή PROVERBS: 1.-Aqueous developer solution, see a photograph! Developer for silver halide and containing a development accelerator, characterized in that the development accelerator is a water-soluble polyoxyalkylened 1,4-butynediol formula R R, r ι I 'ri —J- ¹ 'r — I— ¹ ' - '' ν —— U —— vJ-4— KU-1—11 R ₂ R ₄ represents, in which R is an ethylene or propylene radical, R-, R ₂ , R, and R. each is a hydrogen atom or a lower alkyl group with 1 to 4 carbon atoms and m and η are whole positive numbers whose Suiiaae a Miraestdurch.jchirLttsv / ert before 7 has. 2. Aqueous development according to Ai: -jprueh 1, thereby zaionnet, that the lrt development accelerator na ;, Ir! «r i .. -.m η posi nive ^ ai ^ ze Z-'jiilen cedeut ^ r, whose eir j .:" Dui-uMdch: .it iave. "t before. 7 to 100 .u.1. j. Ytessrige ßi.t. / icirl.jrli '/ iui ^ - j ^ ci. Ar.Sjr ^ cu 1, -J.iiurcn ^ r.eicin.et, iasa the iJrt-.vicivluijgsbe αϋΐβϋΐ.ΐ -er the Jr'oiuel OH, CH ₃ - cn - Cu ₂ CH ₂ - c: i - _{3 2 2} H- £ 0CH ₂ CH JG - C - C ^ C - C - Cr ' CH ₃ 909851/0984 ORIGINAL BATHROOM has, _ in which m and η mean positive integers, their sum has an average of 7 Ms IQO. ,. for General Aniline & film Corporation New York, BT.Y., T.St.A. Lawyer 0 9851/098 U