DE2049289A1 - Color photographic light-sensitive materials with improved lightfastness - Google Patents

Description

PATENT LAWYERS

DR. E. WIEGAND DIPL-ING. W. NIEMANN OfW Q 9 Q Q

DR. M. KÖHLER DIPL-ING. G GERNHARDT 2 U VcJ Z 0

MÖNCHEN HAMBURG

TELEPHONE: 5554 76 ' 8000 MUNICH T5,

TELEGRAMS: KARPATENT NUSSBAUMSTRASSE 10

7 October 1970 W _e 40 121/70 - Ko / B

Photo Film Co, Ltd _e , Ashigara-Kamigun, Kanagawa, Japan

Color photographic photosensitive materials with improved lightfastness

The invention relates to a color photography photosensitive material with improved fastness or resistance to light.

As the color photographic image from the color development formed dyes is built up, the image has poorer lightfastness than a Black-and-white photographic image that is made of metallic silver »There was of course an attempt at this Error due to the removal of the influences of ultraviolet rays to avoid by showing a great destructive effect on dyes of the color image Ultraviolet absorbers have been used and various attempts have been made in which ultraviolet absorbers, which do not leak in the development treatment into the light-sensitive materials were incorporated in their manufacture.

The ultraviolet absorbers used for this purpose are required to have the following properties: j

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1. You must be effective with using ultraviolet emitters Absorb wavelengths of 300 to 4-00 millimicrons, but are allowed to absorb visible light with wavelengths longer does not absorb than 420 millimicrons;

2. They must not leak or become discolored during the development treatment;

3. The ultraviolet absorbers themselves must not be colored or theirs upon exposure to light

^ Decrease ultraviolet absorbance;

W 4, you must not have any bad influences on the

photographic photosensitive materials during the manufacture of photographic photosensitive materials Materials, during their storage and during development.

Numerous types of ultraviolet absorbers are already known, but only a few satisfy them the four factors listed above. Furthermore, many of the commercially available ultraviolet absorbers are used washed out or discolored, and some of them show bad influences on photographic properties of photographic photosensitive emulsions.

| t As a method of avoiding the bad influences of the ultraviolet absorbers on silver halide photographic emulsions is a known method in which dem.a water-insoluble ultraviolet absorbent in a water-insoluble high-boiling organic solvent, e.g., dibutyl phthalate, and then made into a photographic silver halide J . ■ · emulsion is added as an emulsified dispersion, for which purpose Jr- see U.S. Patent No. 2,739,888 3,352,681 will.

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In the course of the investigation of this problem, attention has now been drawn to the incorporation of a water-insoluble oily ultraviolet absorber as an emulsified dispersion in a photographic silver halide emulsion and sought ultraviolet absorbers suitable for this purpose. This ultra ' Violet absorbents must meet the suitability of oily materials in addition to the four factors listed above capable of dispersion in a gelatin sol as a stably emulsified dispersion. From these Different connections have now been considered produced and carried out extensive tests with these and found that compounds according to the following general formula

R-O-

for these purposes are suitable wherein R and R ', the may be the same or different, mean alkyl groups with .1 to 20 carbon atoms, the sum the carbon atoms of the radicals R and R 'is at least 5.

When the above compounds are added to an aqueous gelatin solution containing a surface-active agent Contains agent, are added and the mixture is treated in a colloid mill, becomes a

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Stably emulsified dispersion obtained and by applying a gelatin sol containing the above Contains ultraviolet absorber on a color photographic light-sensitive material ^ as Auxiliary layer, for example as a protective layer, intermediate layer, undercoat or back layer when used a transparent support, the lightfastness of the color photographic image is improved.

Since the application of the inventive ultraviolet. absorbent does not require a solvent for the emulsified "dispersion of the compound, the amount of gelatin used to emulsify the dispersion can be reduced, making the coating and drying processes both economically advantageous and effective in the sharpness of the color photographic image and speed Further, if necessary, the dispersion containing the ultraviolet absorbent of the present invention can be incorporated into photographic light-sensitive silver halide emulsion layers, and in this case the ultraviolet absorbents of the invention do not show a bad influence on the photographic properties ^{1 of} the silver halide emulsion layers.

Usually occurs when using an ultraviolet absorbent Layer at the same time reducing the sensitivity to visible light of the blue / sensitive Emulsion layer on. However, if the invention Ultraviolet absorbers are used, the sensitivity of the blue-sensitive layer becomes not diminished because the connections are practically no

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absorb visible light, and further the sensitivity of the blue-sensitive emulsion layer cut off sharply to ultraviolet rays

will. By curtailing the sensitivity of the

blue sensitive emulsion layer for ultraviolet. can radiate the quality of color rendering based on the difference in ultraviolet absorption properties of camera lenses, to be improved "

The properties of the ultraviolet absorbers listed above according to the invention also emerge from the accompanying drawings.

Fig. 1 is a graph showing the transmittance spectrum curve of a gelatin film, which is an emulsified dispersion with the built-in ultraviolet absorbent according to the invention in one

It contains an amount of 20 mg per 100 cm and, as can be seen from the graph, shows sharp absorption characteristics at 390 to 400 mn. Also in Fig. 2 is a graph showing the spectral sensitivity curves of a sample in which a layer containing the ultraviolet absorbent according to the invention is not on the blue-sensitive. Chen emulsion layer was formed (curve 1), a sample in which a layer containing the ultraviolet absorbent according to the invention is formed thereon (curve 2) and a sample in which a layer containing a known ultraviolet absorbent, 3-cetyl 5-benzal-3rphenyliminothiazolidone, is applied to a blue-sensitive emulsion layer (curve 3), each sample being exposed by means of a spectrophotometer and subjected to color development. As can be seen from these results, the sample with the

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Layer containing the ultraviolet absorbent according to the invention, the sensitivity to the The ultraviolet range is cut off sharply without reducing its sensitivity to the visible range is decreased.

Since the compounds according to the invention are oily materials, the compounds can also be used as solvents for those additives that are made using a high-boiling organic solvent such as dibutyl phthalate, may be added, for example, oily couplers, antioxidants and solid ultraviolet absorbers other than those according to the invention can be used. Optionally, the ultraviolet absorbers can be used according to the invention also used together with a high-boiling organic solvent will. The amount of the compound used in the color photographic material can be determined by the Easily choose professional.

In either case, the application of the oily ultraviolet absorbers is in color photographic photosensitive Materials in various points of view against the addition of ultraviolet absorbents, which are solid at around room temperature, as solutions in high-boiling organic solvents · superior and this is demonstrated in an excellent manner by the Use of the compounds according to the invention is possible.

Below are typical examples of compounds according to the invention corresponding to the above general formula given together with their boiling points.

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Connection 1

CH = C

COC ₁ -H ₁₁ Cn)

it 3 I 0

₁₁

Boiling point: 185-188 ° (/ 0.4 mm Hg

Connection 2

CH = C

CN

COC ₆ H ₁ , (n)

It

Boiling point: 191-192 ° c / 0.38 mm Hg

Connection 3

PC ₂ H ₅

CH = C I

C-O-CH ₂ CH-CH _g

Boiling point: 198-220 ° c / 0.24 mm Hg

Connection 4

'0-0-C ₁₀ H ₂₁ (η)

Boiling point: 243-253 ° ί / 2.4 mm Hg

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Connection 5

ΟΗ, -Ο-Γ ^χ > -CH = C ^

⁵ W / ^ COC ₁₂ H ₂₅ Cn)

O Boiling point: 23Ο-24Ο ° (/ θ, 32 mm Hg-

Connection 6

Boiling point; 220-225 ^c (/ 0.30 mm Hg

The compounds listed above can be prepared from the corresponding cyanoacetic acid esters and alkoxybenzaldehydes can be produced by conventional methods (Beil., Volume 10, page 521).

An example of the preparation is given below: 136 g of anisaldehyde, 197 g of 2-ethylhexylcyanoacetate, 10 g of ammonium acetate and 25 ml of glacial acetic acid were added to 500 ml of benzene. The mixture was heated with stirring to 130 to HO ⁰ C with distilling off water until the formation of the water had ended. After the reaction, 300 ml of benzene was added. The benzene solution was washed with water, dried and the benzene was distilled off. The residue was distilled under reduced pressure, and 270 g of the compound having a boiling point of 198 to 220 ° C / 0.24 mmHg was obtained.

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It is known that compounds similar to the Compounds according to the invention are useful as ultraviolet absorbers, e.g. German U.S. Patent 1,087,902, however, there are no references describing the compounds according to the invention particularly useful as ultraviolet absorbers for color photographic photosensitive materials are valuable. The compounds listed in the above German patent specification are also included Solid at normal temperature and therefore not very useful for the present purposes.

The following examples are provided for further explanation the invention.

example 1 Component Sample A Sample B Sample G

aqueous gelatin solution 10 $ 1 kg 1 kg 1 kg

Sodium dodecylbenzene

sulfonate $ 5 50ml 50ml 50ml

Dibutyl phthalate - 50 ml 50 ml compound 2 50 g 50 g 3-cetyl-5-benzal-

3-phenyliminothia-

zolidon - - 50 g

As can be seen from the table above, 50 g of compound 2 directly to a mixture of 1 kg of a 10% aqueous gelatin solution and 50 ml Seigern added sodium dodecylbenzenesulfonate and that Mixture dispersed by emulsification for 5 minutes in a colloid mill. Then the mixture turned up a triacetyl cellulose base raised and

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dries to give a sample called Sample A.

Then '50 g of the compound 2 according to the invention at room temperature with 50 ml of dibutyl phthalate mixed and after emulsification of the mixture in the above mixture of aqueous gelatin solution and Sodium dodecylbenzenesulfonate dispe.rgiert in the above manner, whereupon the resulting mixture on a Triacetyl cellulose film was drawn up and dried to give a sample called Sample B.

For comparison, 50 g of the known ultraviolet absorbent was used 3-cetyl-5-benzal-3-phenyliminothiazolidone, which has similar ultraviolet absorption properties as the compound 2 according to the invention, mixed with 50 ml of dibutyl phthalate and then dissolved with heating and, after dispersing, by emulsification as above, the resulting mixture became drawn up on a triacetyl cellulose film and dried to obtain a sample referred to as sample C. will.

These samples were compared, Sample C is' right after; transparent, however, forming if the sample is at room temperature for about a month is stored, crystals from and the raised Layer containing the well-known ultraviplet absorbent contains, becomes opaque or cloudy. This crystallization even forms within a day off when the layer is rubbed or a blow is exerted on the layer. On the other hand, they showed Samples A and! B, each as an ultraviolet absorbent contained the compound 2 according to the invention, these disturbances do not. Even if the mixture of

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bond 2 and dibutyl phthalate during manufacture of Sample B was heated, the properties of Sample B were not changed or decreased. If on the other hand a mixture of dibutyl phthalate and the well-known ultraviolet absorbent 3-cetyl-5-benzal " 3-phenyliminothiazolidone is not heated, it will Ultraviolet absorbent not dissolved in the solvent. .

. Each of Samples A to C was exposed to a fluorescent lamp of 10,000 lux for 14 days; the reduction ratio of the absorption maximum can be seen in the following table:

Sample A sample B sample C ,

Reduction ratio of the absorption maximum 29 $ 31 $ 30 $

Even when the samples ^{were stored without exposure to light under conditions of 60 °} C. and 70 ° C. for 14 days, 40 ^° C. and 90 ° C. for 14 days, and 80 ^° C. for 7 days, there was no reduction in the absorption maximum observed. When samples A to 0 of the following treatment were processed with the treatment solution described in The British Journal of Photography, September 27, page 838 (1968), no reduction in the maximum absorption location was observed in the samples; during the treatment the temperature was 30 ^° C.

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development 7th Minutes Stop fixation 2 ti Water washing 2 It bleaching 2 It Water washing CVl It Hardening s f ix i e ration 2 Il Water washing 4th Il stabilization cvi Il

Furthermore, the same procedures as in

* of the preparation of Samples A and B, using Compound · 1 and Compounds 3 to 5, and practically the same results were obtained.

Example 2

A blue-sensitive silver iodobromide emulsion containing benzoylaceto-2-chloro-5-dodecylcarbonylanilide as a yellow coupler, a gelatin sol as an intermediate layer, a green-sensitive silver chlorobromide emulsion, the 1-phenyl-3-amiao-propionylcaprylamide ~ pyrazolone as W magenta coupler containing a gelatin sol as an intermediate layer and a red-sensitive silver chlorobromide emulsion containing 1-hydroxy-2- / 3 '-, mounted (2 ¹ contained, 4'-t-aiainophenoxyjpropyV-naphthamide as cyan couplers in this order each of the couplers. had been prepared for the photographic emulsion by dissolving the coupler in dibutyl phthalate, emulsifying the solution in an aqueous gelatin solution and then adding the emulsified dispersion to the photographic, phical ^, emulsion., fi ν -; ί

1,098 1 6 /

An emulsified dispersion, which corresponded in each case to samples A to C according to Example 1, was then coated on the red-sensitive emulsion layer as a protective layer so that the proportion of the ultraviolet absorbent Was 20 mg / 100 cm. The color photographic photosensitive film known as Protective layer sample A according to Example 1 without application of dibutyl phthalate is used as sample Ξ, the color photographic photosensitive film accordingly the sample B becomes sample E and the color photographic light-sensitive film corresponding to the Sample G is referred to as Sample F. For comparison purposes was also a color photographic photosensitive film with a protective layer composed only of gelatin sol and this sample is named Sample G.

When these samples were compared, it was found that the sample F easily crystallized and the sample material of sample C is therefore not suitable for use as a protective layer, while such disturbances occur Samples D and E did not occur, so Samples A and B, which are the ultraviolet absorbers according to the invention especially to prevent fading or fading of color photographic photosensitive materials are suitable.

If the film samples produced in this way were subjected to the photographic treatment given in Example 1 and irradiated with a fluorescent lamp of 10,000 lux for H days, It was shown that the lightfastness of Samples D and E each having a protective layer with an ultraviolet absorbent according to the invention was that

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the sample G- was superior, as can be seen from the following Table shows, with the numerical values representing the fading ratios expressed as a percentage of the color images at a density of 1.0.

Sample D Sample E Sample F Sample G.

Yellow IO56 1056 IO96 20 $ Magenta 20% 20% 20 $ 40% Cyan 5% 5% 5% 10%

Although the sample F is similar to the other samples immediately after the treatment, crystals form on the surface of the sample after days, so that the surface is matted. Even if the samples are stored for 14 days at a temperature of 60 ^c C and a relative humidity of 70 ⁰ C and for 14 days at a temperature of 40 ^c C and a relative humidity of 90% the extent of the change in the density of the color image is practically the same as in Samples D to G. However, when working under the conditions of 80 ^° C and 7 days with Sample F crystallized, no change is made in Samples D, S and G observed.

In this experiment, the emulsified dispersion of the ultraviolet absorbent was used as it was as Protective layer is used and the dispersion can be added to a gelatin solution. The same procedure as above was repeated using compounds 1, 3, 4 or 5 and they became practically the same Results as for Samples D and S were obtained.

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Even if a transparent film in the above Method is used in place of the barite-coated paper, the same results are obtained.

Example 3

The blue-sensitive silver iodobromide emulsion, which is a yellow coupler contained, and the gelatin sol as an intermediate layer, as in Example 2, absorbed. On the intermediate layer a red-sensitive silver chlorobromide emulsion was drawn up and the emulsified dispersion contained the following composition:

Sample H Sample I Sample J

aqueous gelatin solution ($ 10)

Sodium dodecyl benzene sulfonate (5 °)

i-Hydroxy-2- ^ '(2 ·, 4 L-t-amylphenoxy) propyl / naphthamide

Dibutyl phthalate

Compound 3 50 g -

3-cetyl-5-benzal-3-phenyliminothiazolidone -. 50 g

The red-sensitive emulsion layer was also applied successively a gelatin sol as an intermediate layer, the green-sensitive silver chlorobromide emulsion, which contained the magenta coupler, and then applied a gelatin sol as a protective layer.

1 kg 1 kg ml 1 kg 100 ml 100 G 100 ml 100 g 100 ml 100 g 150 ml 250 200 ml

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The emulsified dispersion with that in the above The composition given in the table was prepared in the following manner: A solution of the cyan coupler and the ultraviolet absorbent in dibutyl phthalate prepared by heating the mixture became a mixture of 1 kg of a 10% aqueous gelatin solution and 100 ml of sodium dodecylbenzenesulfonate added and then the resulting mixture emulsified for 5 minutes in a colloid mill. As can be seen from the table above, in the case of sample I, in which the cyan coupler must be combined is used with the known ultraviolet absorbent, the amount of the dibutyl phthalate serving as a solvent can be increased according to the amount of the ultraviolet absorbent to be added, while im Pail of sample H, in which the compound of the invention was used together with the cyan coupler, the amount of the solvent according to the increase in the amount of the ultraviolet absorbent could be reduced, so that the present invention is very advantageous will. ·

If the specimens of the photographic processing according to The Journal of the S.M.P.T.E., Volume 61, No. 12, Page 667 (1953) and then exposed to a fluorescent lamp of 10,000 lux for 14 days It was found that the color photographic film according to the invention wherein couplers and ultraviolet absorbents according to the invention were simultaneously dispersed by emulsification, one effective anti-fading effect was shown, as can be seen from the following table, in which the numerical values represent the fading ratios of color images at one density

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of 1.0 are given.

Sample Ή Sample I Sample J

yellow $ 10 $ 10 $ 20 Cyan $ 7 $ 8 $ 10 magenta $ 40 $ 40 $ 40

Even when the samples were stored for 14 days at a temperature of 60 ^° C. and a relative humidity of 70 °, for 14 days at a temperature of 40 ^° C. and a humidity of 90 ° and for 7 days at 80 ^{° C.} the samples made similar changes.

Thus, when the ultraviolet absorbent according to the invention can be emulsified together with a magenta coupler or a yellow coupler, valuable results can be obtained. The ultraviolet absorbers according to the invention can also be effective in a different order of photographic Layers are used as those for the above-mentioned color photographic light-sensitive materials.

From the above description it is clear that when emulsified dispersions containing the Ultraviolet absorbers according to the invention contain to photographic silver halide emulsion bags or auxiliary layers, such as protective layers, intermediate layers, undercoats and, if a transparent one Basis is used, backing layers is added, the light fading of the color image the photographic silver halide emulsion

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layer containing the ultraviolet absorbent according to the invention or the color image of a photographic one Silver halide emulsion layer constituted by a layer containing the ultraviolet absorbent according to the invention is covered can be effectively prevented.

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Claims (10)

Claims '' Color photographic photosensitive material, consisting of a support and a photographic layer containing a compound according to the general. formula wherein R and R ', which are the same or different can mean alkyl groups having 1 to 20 carbon atoms, the sum of the carbon atoms being the Radicals R and R 'is at least 5 contains. 2. Color photographic photosensitive material according to claim 1, characterized in that the photographic ' Layer consists of a photographic silver halide emulsion layer. 3. color photographic photosensitive material, according to claim 1, characterized in that the photographic layer consists of a protective layer. 4 »Color photographic light-sensitive material according to claim 1, characterized in that the photographic Layer consists of a back layer. 5. color photographic photosensitive material, consisting of a support and a photographic layer which has a νβΓΐ> 1ηαμη§ of the formula - 0 -. C ₅ H ₁₁ (Ii) contains. . 109816/1916 6. A color photographic light-sensitive material composed of a support and a photographic one Layer that is a compound of the formula CN , - 0 - // V ^CH = ^c C S - ° - ^C 6 ^H i3 ⁽ⁿ⁾ contains. 7. A color photographic light-sensitive material composed of a support and a photographic one Layer that is a compound of the formula CN C ₂ H _{5 3} - o -r Vch = he j -O- CH ₉ CH - C.Hq ^{4 9} ο contains. 8 * Color photographic light-sensitive material composed of a support and a photographic one Layer that is a compound of the formula CH, - 0 -V n_CH - CN
CO contains. 1098 16/1916 A i. Γ Γ \ 9. color photographic photosensitive material; consisting of a support and a photographic layer which is a compound of the formula CN CH ₃ - 0 -Γ Λ- CH = C 0 contains. 10, color photographic photosensitive material, consisting of a support and a photographic layer which is a compound of the formula OCN_ CH = C ^ ^X C-0 contains. 10 9 8 16/1916 Blank page