JPS5826016B2 - Shashinyouso - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to novel photographic elements containing 1-amino-4-cyano-1,3-butadiene compounds as filter compounds.

The compounds used in this invention possess properties that absorb ultraviolet light (UV light) and convert them into effective filter dyes.

Although it is clear that these UV-absorbing compounds are primarily useful with color films and papers containing photoreducible silver halide, they may optionally contain photoreducible silver halide. It is also possible to incorporate it into black and white films.

As known to those of ordinary skill in the photographic arts, silver halide emulsions possess sensitivity to ultraviolet light.

Unless provided with protection from ultraviolet light, color films such as Kodachrome and Eftachrome films will be adversely affected by ultraviolet light.

For example, if ultraviolet light is not substantially prevented from reaching the silver halide-containing layer of a color film as described above, such film will produce an image that is more bluish than it actually is. will.

In a photograph taken using a film without a UV-absorbing filter layer, for example, snow or an asphalt road will appear unnaturally bluish in color or image.

As can be seen from the above brief explanation and discussion, in order to obtain color photographs with true colors, it is better to prevent ultraviolet light from reaching the silver halide-containing layer of the color film.

Attempts have been made to use various materials as UV absorbers in photographic elements, particularly in the overcoats of such elements.

Water-soluble UV absorbers can diffuse into other photographic element layers during coating and processing, which can sometimes adversely affect various photographic functions.

On the other hand, when evaluating water-insoluble UV absorbers, a common solvent is usually required to disperse them in the photographic emulsion.
Moreover, the systems obtained in this way are always unstable.

That is, if left undisturbed, the oil phase often separates.

After coating, the dye aggregates and the coated layer exhibits new and undesirable absorption shoulders.

The conventionally preferred method for dispersing water-insoluble substances in aqueous gelatin coating compositions is to disperse such water-insoluble substances in (1) a high-boiling organic solvent (
(which will not evaporate from the coated layer) and (11) optionally also an auxiliary solvent, and the solution is subsequently milled with an aqueous gelatin solution in a colloid mill for a considerable period of time to satisfy the This included preparing several coating compositions.

This dispersion subsequently had to be transformed into noodles and washed to remove the co-solvent.

This process was complex, time consuming, ineffective, and exothermic.

In addition, the resulting dispersion has a tendency to coagulate, agglomerate or crystallize, and the oil in the coating layer drawn therefrom has a tendency to migrate or diffuse into other layers.

The compounds used as ultraviolet filter compounds in this invention have a high degree of absorption capacity.

These UV absorbing compounds are generally low melting point solids;
It is pure in liquid form.

These compounds strongly absorb wavelengths up to 400 nm, while exhibiting only slight absorption beyond 400 nm.

These compounds are unexpectedly stable even when exposed to heat.

Although these compounds are hydrophobic when in liquid form, they can also be incorporated directly into other conventional photographic polymeric supports.

These compounds can furthermore be used together with binders as coating compositions.

In this case, the coating composition can be applied as a separate layer on the photographic support, and the use of special or auxiliary solvents, if necessary, is unnecessary.

The UV absorbing compounds used in this invention include compounds represented by the following general formula (I).

In the above formula, n is 1 or 2, and when n is 1, R
1 and R2 may be the same or different from each other,
Hydrogen, alkyl groups having 1 to 10 carbon atoms, including substituted alkyl groups such as cyanoalkyl groups and alkoxyalkyl groups, aryl groups having 6 to 20 carbon atoms, including substituted aryl groups, or cyclic alkyl groups; and when they are combined and integrated, R1 and R2 are a cyclic amino group, such as a piperidino group,
Represents an atomic group necessary to complete a morpholino group, pyrrolidino group, hexahydroazepino group, and piperazino group, provided that in this case, neither R1 nor R2 can be hydrogen, and furthermore, when n is 2 R1 and R2 represent an alkylene group or an arylene group, and G is an electron-absorbing group, such as CN or 5O2R (wherein R is an alkyl group having 1 to 10 carbon atoms or an arylalkyl group having 7 to 15 carbon atoms). is a group).

The UV-absorbing compounds used in this invention are prepared in accordance with conventional methods, first by first treating a suitable primary or secondary amine with a suitable intermediate in absolute alcohol (at the reflux temperature of the resulting solution); It is prepared by distilling the resulting product under reduced pressure.

In this way, the target compound can be obtained in high yield and with high purity.

One of the inventions of this application is a photographic element, which includes a photographic support containing therein at least one UV absorbing compound having the structure of general formula (I). There is.

When a material for UV absorption is used in a photographic element, it is generally desirable for the support to be transparent if the material is incorporated within a support, and usually the support is substantially colorless. It is preferable that

A variety of conventional transparent photographic film supports are known in the art as suitable supports into which UV absorbing compounds can be incorporated.

For purposes of discussion, these photographic supports can be divided into broad categories: those that can be solution cast and those that are produced from a melt.

UV absorbing compounds are stable and can be incorporated into photographic elements without the use of special or auxiliary solvents.

To incorporate a UV-absorbing compound into a solution-cast film support, such as a cellulosic support, such as one composed of cellulose nitrate, cellulose diacetate, cellulose triacetate, etc., the compound is simply added to the support. It is only necessary to dissolve it in the casting solution used for production.

UV absorbing compounds can also be incorporated into polymeric film supports prepared from the melt.

In this case, incorporation of the compound can be accomplished simply through dispersing the dye into the molten polymer.

The UV-absorbing compounds have good thermal stability and are therefore suitable for film support materials prepared from the melt, such as polyalkylenes (e.g. polyethylene), polystyrene, phthalic polyesters, e.g. poly(ethylene terephthalate), polycarbonates as well as film supports. It can be blended with other low-melting point resinous polymers useful in the manufacture of polymers.

Generally, it is advantageous to have the UV absorbing compound substantially uniformly dispersed within the film support so as to provide a uniform optical density when viewing the support.

This can be easily accomplished through thorough mixing of the UV absorbing compound and the support material (prior to forming it into a support) using techniques well known in the art. .

In another invention, a UV absorbing compound is coated in the ultraviolet filter layer of the photographic element.

In this usage, it is of course possible to use any of the conventional photographic supports.

The support in this case can be opaque or transparent.

This support can optionally have a variety of different forms, including glass, metal, film, wood, paper or composite (eg resin-coated paper) supports.

In order to spatially immobilize a UV-absorbing material on a support, it is generally advantageous to incorporate it inside a transparent layer containing a binder and in direct association with the support. It is.

Sometimes the binder may be the same type of polymer that makes up the support.

This compound can also be incorporated into any photographic binder layer if desired.

In general, any conventional transparent binder can be used.

Particularly useful classes of binders include, for example, British Patent No. 1
．． These latexes are disclosed in US Pat. No. 504,950.

This British patent has yet another important method, namely the U.
Also disclosed are methods that can be applied in incorporating V-absorbing compounds into photographic elements or emulsions.

Furthermore, if necessary, a hydrophilic colloid such as gelatin can also be used as a binder material.

Containing one or more types of UV absorbing materials 1
The one or more binder layers can be placed directly on the support or can be separated by one or more subbing layers provided for the purpose of improving adhesion to the support. can.

Such a binder layer may also be present as an overcoat or overcoat layer over one or more emulsion layers, if desired.

A binder layer containing one or more UV-absorbing compounds can be applied as an underlayer and optionally as an overcoat layer on a single support.

Examples of other suitable photographic vehicles and layer arrangements useful as binders can be found in Product Licensing Index, Volume 92, December 1971, Publication 9232.10.
It is described on page 8, section ■.

Generally, the UV absorbing compounds in the binder layer as contemplated herein are selected to produce optical densities similar to those described above with respect to UV absorbing compounds incorporated into the support.

An optically homogeneous dispersion of the compound in the binder is advantageous, and this can be obtained without the use of auxiliary solvents.

This can be accomplished by the techniques disclosed in the above-mentioned British patents as well as techniques known in the art.

These UV absorbing compounds can be used in photographic elements containing silver halide emulsions.

These compounds can also be incorporated into silver halide emulsion layers.

Silver halide emulsions include silver chloride, silver bromide, silver bromoiodide,
It can be composed of silver chlorobromide, silver chloroiodide, silver chlorobromoiodide crystals, or a mixture thereof.

These emulsions can be coarse grain or fine grain emulsions and can be prepared by a variety of techniques.

These emulsions include, for example, single jet emulsions, double jet emulsions, ammonia emulsions, and thiocyanate or thioether ripened emulsions.

These silver halide emulsions can form latent images primarily on the surfaces of their silver halide grains or primarily within their silver halide grains.

If desired, a mixture of a surface-type image-forming emulsion and an internal-type image-forming emulsion as described above can be prepared.

These silver halide emulsions are emulsions with regular grain sizes,
It can be a negative-working emulsion as well as a direct positive-working emulsion.

Preferably, UV-absorbing compounds are used in elements made for color photography, such as elements containing silver halide emulsions and color-forming couplers, elements to be developed in solutions containing color-forming couplers, and sensitized color materials. can do.

UV absorbing compounds can be added to photographic elements such as those described in U.S. Pat. No. 3,761,276 and U.S. Pat.
For example, US Patent No. 2352014, US Patent No. 254318
No. 1, US Pat. No. 3,020,155 and US Pat. No. 2,861,885, silver halide diffusion transfer-free elements in which silver halide development proceeds using processes such as those described in US Pat. No. 3,087,817 and US Pat. No. 3,185,567 , same second
No. 983606, No. 3253915, No. 3227
No. 550, No. 3227551, No. 3227552
No. 3415644, No. 3415645, No. 3415646, No. 2543181 and No. 3
No. 635,707, Canadian Patent No. 674,082, and Belgian Patents No. 757,959 and Belgian Patent No. 757,960, and elements for color image transfer processes such as those described in U.S. Pat. Can also be used for elements.

In photographic elements made for use in color photography, U is incorporated in a binder layer as an overcoat over the photosensitive layer(s) to be protected.
Preference is given to using V-absorbing compounds.

These UV-absorbing compounds can also be used as intermediate layers, ie layers below layers that do not require protection.

These UV compounds may also be incorporated into the support or otherwise applied prior to applying the light-sensitive emulsion layer to the support to minimize the reflection of light at the surface of the support. The support may also be provided with a single layer of UV-absorbing filter.

The preparation of useful UV-absorbing compounds is then described in Preparation Example A-
This will be explained in P.

Intermediate Preparator Intermediate 3-acetanyl biarylidene malononitrile: was prepared by preparing malononitrile (50
g) was prepared by heating under reflux for 10 minutes with 3-anilinoacroleinanil (186g).

The solution thus obtained was then cooled and filtered, and the resulting solid was washed in methanol.

The resulting product was recrystallized from acetic anhydride, filtered, and the resulting solid was washed with methanol and dried.

Yield was 110g.

B Intermediate 3-Methoxyallylidenemalononitrile: Malononitrile (132,!li+, 2.0 mol) and trimethoxypropene (270,!li', 2.0 mol) were dissolved in 250 rILl petitonitrile over 1 hour. Prepared by heating under reflux.

The resulting solution was then cooled in dry ice to obtain the desired product.

Yield was 65g (25%).

Preparation of UV Absorbing Compound A 3-Dibutylaminoallylidenemalononitrile dibutylamine (15.0 g, 0.116 mol) was added to the intermediate of Preparation A: 3-acetanilide allylidenemalononitrile (11.9 g, 0.05 mol) in ethanol (50, ml) for 20 minutes.

Next, ethanol was distilled off and distillation was carried out at a temperature of 157°C and 3 μm to obtain the desired product.

Molecular weight 231.33, C14H2, N3, yield 5.01
4s bun) B 3-dihexylaminoallylidene malononito dihexylamine (20.0 g, 0.108 mol) was converted into 3-acetanilide allylidene malononitrile (11,9,91
2 in ethanol (50 mA) with 0.05 mol)
Refluxed for 0 minutes.

The ethanol was then distilled off at a temperature of 170°C and 5μ
Distillation was performed to obtain the desired product.

Molecular weight = 287.43, Cl8H2GINS, yield 4.
8.9 (Article 33) C3-tert--butylaminoallylidene malononitrile tert,-butylamine (50 fIX 0.68 mono-3-acetanilide allylidene malononitrile (6
,0 g, 0.29 mol) together with ethanol (300
refluxed in rILl) for 15 minutes.

After quenching, the desired compound was precipitated from the reaction mixture and then purified by recrystallizing the mixture from ethanol.

Molecular weight = 175.24, yield 15. (1 (Article 30) D 3-diisobutylaminoallylidenemalononitrile diisobutylamine (25 g, 0.20 mol) was converted into 3-acetanilideallylidenemalononitrile (23,0,!
li', 0.10 mol) together with ethanol (50 m
The mixture was refluxed for 15 minutes in a vacuum.

Next, ethanol was distilled off and distillation was carried out at a temperature of 124 to 160° C. and 4 μm to obtain the desired product.

Molecular weight = 231.33, C14H21N3, yield 9.5
g (section 41).

E 3-disec,-butylaminoallylidenemalononitrile di5ec--butylamine (25&, 0.20 mol) was converted into 3-acetanilideallylidenemalononitrile (
23,0 g, 0.10 mol) together with ethanol (10
01rll) for 20 minutes.

Next, ethanol was distilled off and distillation was carried out at a temperature of 150° C. and 6 μm to obtain the desired product.

Molecular weight = 231.33, C14H2□N3, yield 4. '
1 (more than 20).

F 3-Hexahydroazepine arylidene malononitrile Hexahydroacepine (20.0 g, 0.02 mol) was converted into 3-acetanilide allylidene malononitrile (11,
(1,0,05 mol) together with ethanol (501 rL
1).

Next, ethanol was distilled off and distillation was carried out at a temperature of 150 to 180°C and 3 μm to obtain the desired product.

Molecular weight = 201.24, C1□H15N3, yield 4.9
Intermediate of Preparation Example B, 3-methoxya IJ IJ denmalononitrile (13,4,!ii')
-Butyl-N-cyanomethylamine (13g) was heated.

This solution was then distilled to collect fractions boiling at temperatures of 140-1172°C and 8μ.

Yield 11.59゜ The intermediate of Preparation Example A above was converted into the following amines: (a) bis(2,2-jethoxyethyl)amic (b) N-cyanomethyl-N-methylamine hydrochloride (c) piperazine (d ) N,N-Diethyl-1,6-hexaneamine (e) was used with bis(2-cyanoethyl)amine to prepare compound (H-N) as described below.

H3(N,N-bis-(2,2-jethoxyethyl)amino)allylidenemalononitrile L3-(N,N-bis(2-cyanethyl)aminocoarylidenemalononitrile Compound M-P is 3 respectively types of reactants, i.e., a suitable amine and a suitable sulfonylacetonitrile and 1.1
．． Prepared by co-refluxing 3-1rimethoxypropene.

The specific reactants used herein are listed in Table 1 below.

Compounds N, 0 and P precipitated during reflux or after subsequent cooling.

Compounds N and O were treated with an alcohol, such as ethanol or isopropanol, as an addition step, as a result of which the precipitate could be easily filtered.

Compound N was purified by dissolving it in cresol and reprecipitating it by adding methanol.

Compound O was purified by passing a methanol/acetonitrile solution of the compound through a column (containing Amberlyst ion exchange resin).

Compound P was washed with ether, then the compound was redissolved in acetone, ether was added until the resulting solution became cloudy, and the purified compound was washed for 7 hours before being collected.
Purification was achieved by rapidly cooling the suspension for 2 hours.

Compound M was very difficult to separate.

This compound did not precipitate directly from the reaction mixture.

For this purpose, a portion of the reaction mixture was removed, stirring was continued until crystals formed, and the crystals thus formed were then used as seeds for the reaction mixture.

Ethanol was added and the resulting product was harvested and recrystallized from methanol.

M 3-morpholinoarylidenemethylsulfonylacetonitrile A part of the UV absorbing material prepared in the above preparation example was mixed with methanol to obtain a solution.

The calculated Nakamoto absorption maximum (λ) and extinction coefficient ( ax As shown in Table 2.

'max) below Next, the evaluation of useful UV absorbing compounds in photographic layers is illustrated in the following examples.

Example 1 UV compound of Preparation Example A (3-dibutylaminoa IJ
IJ denmalononitrile) was dispersed in a gelatin emulsion without the use of co-solvents and then diluted with dry gelatin at 0.9
It was applied to obtain a coverage of 8 g/d and 0.27 g/- of UV compound.

This emulsion was coated on a cellulose acetate film support and the absorption maximum (λmax) of the coating was found to be the same as in methanol solution (377 nm).

Example 2 The optical density of the UV compound of Preparation B (3-dihexylaminoallylidene malononitrile) was measured on a series of coatings.

Example 2(b) was a solventless/gelatin dispersion of this UV compound.

Example 2(C) is a di-n-butyl phthalate/gelatin dispersion of this UV compound, and Example 2(d) is a ``weighted'' (1o
It was a dispersion of UV compounds in the form of lux.

To this end, in the latter case (Example 2d) the UV compound is contained in the solid particles of a polymer latex composition prepared as disclosed in the aforementioned British Patent No. 1.504,950. Ta.

A dispersion of "bulking" latex particles was prepared by dissolving 40.1 of 3-dihexylaminoallylidene malononitrile in 700 CC of acetone, then adding 1320 g of latex, poly(n-butyl methacrylate to 2-acrylamido-2-methyl Propanesulfonic acid-2-acetoacetoxyethyl methacrylate (85:10:5) was prepared by slowly adding rice to the above UV compound/solvent solution with stirring.

Acetone was removed for 24 minutes at a temperature of 50°C.

Example 2(a) was a gelatin coating containing no UV compounds.

The above data show that coatings of UV compound-containing compositions in the form of gelatin and especially extended latex exhibit excellent UV light absorption, with 415
It shows that it has a very sharp cut-off at nm.

One photographic element according to the invention will now be described.

Multilayer color negative coatings were prepared as described in U.S. Pat. No. 3,046,129, column 25, line 67 to column 26, line 20.

A UV absorbing layer was applied above the blue sensitive layer of this coating.

Note that the ultraviolet absorbing layer used herein contained an extended latex of the compound of Preparation Example B (2.2 g in Latex 40.1) in the latex of Example 2 prepared as described in Example 2 above.

The resulting layer contains 0.119/m' of UV compound and 0.9
Sufficient gelatin was added to the dispersion to contain 0 g/m'' gelatin.

A protective gelatin overcoat was applied above the UV absorbing layer.

A control coating was also prepared which was identical in all respects except that the UV absorbing layer was omitted.

Coating samples were exposed to an unfiltered simulated daylight source using an Eastman IB sensitometer.

Other samples were exposed to the same light source through a Kutten 18A filter, and still other samples were exposed to the same light source through a 977
72 people were exposed through the filter.

These coatings were processed to obtain color negatives according to procedures similar to those described in U.S. Pat. No. 3,046,129, column 23, line 35 to column 24, line 24.

The Kututen 18A filter allows only ultraviolet and infrared light to pass through, while the Latte 72 filter absorbs ultraviolet light up to 405 nm but transmits light in that range at wavelengths above 405 nm.

Table 4 below shows the blue-sensitive layer sensitivity difference (Jl
ogE).

In the case of exposure through a 97772 filter, there is no UV radiation in the exposing radiation and, as expected, the log E obtained for elements with UV-absorbing layers and for elements without UV-absorbing layers. There was no difference between them.

In the case of exposure through a Kutten 18A filter, only ultraviolet and infrared radiation is included in the exposure radiation, and between the log H obtained in the case of elements with a UV-absorbing layer and in the case of elements without a UV-absorbing layer There was a big difference.

This indicates that the ultraviolet absorbing layer effectively removes the ultraviolet rays contained in the exposure radiation.

JlogE* - log exposure of the blue-sensitive layer of the test film for log exposure control

Claims (1)

[Scope of Claims] 1 Comprising a support having at least one silver halide emulsion layer and a UV filter layer thereon, the UV filter layer comprising a binder and at least one compound represented by the following formula: : In the case of 1, R1 and R2 may be the same or different from each other and represent hydrogen, an aryl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a cyclic alkyl group,
Furthermore, when they are combined and integrated, R1 and R2 represent an atomic group necessary to form a piperidino group, a morpholino group, a pyrrolidino group, a hexahydroazepino group, or a piperazino group; however, in this case, R1 and R2 cannot both be hydrogen, and roughly speaking, when n is 2, R1 and R2 represent an alkylene group or an arylene group, and G represents an electron-withdrawing group). element. 2 comprising at least one silver halide emulsion layer coated on a support, said support having at least one ultraviolet filter compound represented by the following formula incorporated therein: n is 1 or 2, and when n is 1, R1 and R2 may be the same or different from each other, hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms; Alternatively, it represents a cyclic alkyl group, and when they are combined and integrated, R1 and R2 represent an atomic group necessary to form a piperidino group, a morpholino group, a pyrrolidino group, a hexahydroazepino group, or a piperazino group. However, in this case, neither R1 and R2 can be hydrogen, and roughly speaking, when n is two, R1 and R2
represents an alkylene group or an arylene group, and G represents an electron attraction difference.