DE3410639A1 - LIGHT-SENSITIVE COLOR PHOTOGRAPHIC SILVER HALOGENIDE MATERIAL - Google Patents

Description

¹ T 54 431

Applicant: Konishiroku Photo Industry Co., Ltd.

No. 26-2 Nishishinjuku 1-chome Shinjuku-ku Tokyo / Japan

Silver halide color photographic light-sensitive material

The invention relates to a photosensitive color photographic material High sensitivity silver halide material capable of providing high quality images, it particularly relates to a photosensitive color photographic material A silver halide material which is excellent in image sharpness, graininess and excellent Has interframe effect as well as high sensitivity.

25 of silver halide color photographic light-sensitive materials (hereinafter referred to as "photosensitive material") is required today to have high sensitivity and provide excellent image quality. In recent years, in particular, there has been a

The need for a photosensitive material is increasing rapidly with a higher sensitivity and an even better image sharpness, graininess and inter-image effect, there the number of photographs taken in rooms under unfavorable room lighting conditions increase and with the light-

35 Sensitive material for use in photography there is a tendency to shrink the format. So far, however, it has been very difficult to do both the

to satisfy desired improvements in terms of sensitivity as well as image quality.

In order to improve sensitivity B and the like in photosensitive materials, for example, the following method is known known, for a part or all of the light-sensitive emulsion layers, a highly sensitive silver halide emulsion layer containing substantially the same color-forming nondiffusible coupler (hereinafter referred to as "highly sensitive emulsion layer") and a low-sensitivity silver halide emulsion layer (hereinafter referred to as ^H low-sensitivity emulsion layer " These emulsions have the same color sensitivity and have a separately stacked layer structure the problem that when the photosensitive material is exposed to light, the light to be picked up by the emulsion layer located closer to the support is absorbed by the emulsion layer located further away from the support and that besides during the Developing the photosensitive material, the developing agent takes time to diffuse to reach the emulsion layer, which is closer to the support. That is, with such a structure, it is difficult to increase the sensitivity of the green-sensitive and red-sensitive emulsion layers disposed in the lower positions in the structure because of the loss of exposure light and the delay in development. 35

On the other hand, US Pat. No. 3,663,228, for example, already discloses a method for changing the coating sequence of the emulsion layers which the structure comprises,

* ben, in which, as in Fig. 1c of this patent In the accompanying drawings, (a) the coating is shown in the order calculated from the carrier the side closer to the support is the following: red-sensitive, green-sensitive and blue-sensitive emulsion layers with low sensitivity and (b) the coating in the order from the side of the carrier calculated on the side farther away from the carrier the following is: red-sensitive, green-sensitive and blue-sensitive Emulsion layers with high sensitivity. With this method it is possible to achieve a higher sensitivity in photosensitive materials than for light-sensitive materials with a layer structure with the regular arrangement given above, although this was not intended, the sensitivity How to improve from the use of an "ND (Neutral Density) Filter" between the above Unit of highly sensitive emulsion layers and the Unit of emulsion layers with low sensitivity emerges.

On the other hand, in U.S. Patent 3,658,536, as shown in Fig. 5 of the drawings accompanying this specification, described a method in which the

² ^ lhe emulsion layer, which has a strong influence on the brightness (gloss), is arranged in the direction of the surface side which is farthest from the support, in order to thereby solve the problem of light loss when the layer is exposed, but there are no indications therein to methods for increasing the sensitivity of the blue-sensitive layer and besides the improvements mentioned in this patent with regard to image sharpness, graininess and the interimage effect

cannot be considered sufficient. 35

In addition to the above-mentioned methods of changing the structure, Japanese Patent Laid-Open No. 49 027/1976 and 97 424/1978 (hereinafter referred to as "Japanese OPI Patent Publication

cations ") and in U.S. Patent 4,129,446 such Methods described. The methods described in these publications result in a higher sensitivity than the light-sensitive materials having the above-mentioned regular arrangement coating structure, they provide however neither green-sensitive nor red-sensitive Emulsion layers with sufficient sensitivity still sufficient improvements in terms of image quality, such as graininess, image sharpness and the like.

It is therefore the main object of the present invention to provide a light-sensitive material having blue-sensitive, green-sensitive and red-sensitive emulsion layers in which all emulsion layers are emulsion layers with the same high sensitivity acts. Another object of the invention is to provide a photosensitive material which has an excellent Sharpness, graininess and excellent inter-image effect as well as high sensitivity. Other objects, features and advantages of the invention will appear from the following description.

It has now been found that the above objects according to the invention can be achieved in that in a photosensitive material with a carrier on which is applied are at least one green-sensitive emulsion layer and at least one red-sensitive emulsion layer and a plurality of blue-sensitive emulsion layers with different sensitivity, the plurality of blue-sensitive emulsion layer comprises a blue-sensitive emulsion layer of higher sensitivity, the on the side furthest from the support, and a blue-sensitive emulsion layer with lower sensitivity, with between the blue sensitivity The emulsion layer with higher sensitivity and the blue-sensitive emulsion layer with lower sensitivity at least one green-sensitive emulsion layer and at least one red-sensitive emulsion layer

1 and that also at least one emulsion layer the group consisting of the two blue-sensitive emulsion layers and the green-sensitive and red-sensitive emulsion layers sandwiched between the blue-sensitive Emulsion layers is arranged, monodisperse silver halide grains contains, and that at least one layer of the green-sensitive emulsion layers. the one between the two ■ blue-sensitive emulsion layers are arranged, contains a magenta coupler.

Preferred embodiments of the invention are those in which:

1) The layer containing the monodisperse silver halide grains contains at least the blue-sensitive high-sensitivity emulsion layer and / or the green-sensitive emulsion layer with high sensitivity according to the invention,

2) it is preferred that all photosensitive emulsion layers, constituting the photosensitive material of the present invention contain monodisperse silver halide grains,

3) In addition, the monodisperse silver halide grains are those of the core-shell type. are (including those of the double core-shell type), and

4) the layer structure of the photosensitive according to the invention Materials red-sensitive, green-sensitive and blue-sensitive emulsion layers with low sensitivity deducted from the carrier in the order mentioned and also red-sensitive on these emulsion layers, green sensitive and blue sensitive emulsion layers with high sensitivity in the order listed having.

The present invention is explained in detail below.

In the photosensitive material of the present invention is the difference in sensitivity between the

" 4 G -

1 of the above emulsion layers with high sensitivity and the above-mentioned low sensitivity (low sensitivity) emulsion layers 0.2 to 1.0 logE (E = exposure) and preferably 0.3 to 0.6 logE, taking into account their graininess and gradation. When emulsion layers with medium sensitivity are provided, according to the invention is the difference in sensitivity between the emulsion layers with medium sensitivity and the emulsion layers with high sensitivity 0.1 to 0.5 logE, and the difference in sensitivity between the emulsion layers with medium sensitivity and the emulsion layers with low sensitivity (low sensitivity) is 0.1 to 0.5 logE.

In addition, it is desirable that the above-mentioned emulsion layer having high sensitivity and the above-mentioned one Low sensitivity emulsion layer essentially have the same spectral sensitivity and that, after color development, the above two emulsions are photographic nondiffusible Contain couplers capable of forming a dye having substantially the same hue.

At least one layer of each of the red-sensitive emulsion layers and the green-sensitive emulsion layers (hereinafter referred to as the red-sensitive emulsion layer of the present invention or green-sensitive emulsion layer according to the invention is between the low-sensitivity emulsion layer and the emulsion layer with high sensitivity of the blue-sensitive according to the invention Emulsion layers are provided, and in this case the green-sensitive emulsion layer of the present invention is useful arranged further away from the support than the red-sensitive emulsion layer according to the invention. A such a structure enables. the green-sensitive emulsion layer, those who. Brightness (gloss) strongly influenced, reducing the influence of light scattering.

, A 7 -

ment by the silver halide cells in the above arranged layer are included, and it also allows the expectation that to some extent blue Light is cut off by the magenta coupler contained in the green-sensitive emulsion layer, the between the high-sensitivity and low-sensitivity blue-sensitive emulsion layers of the present invention is arranged so that the structure is suitable for improving the resulting image sharpness.

Each green-sensitive emulsion layer of the present invention and red-sensitive emulsion layer may be coated in a form of not less than two separate layers and each of the blue-sensitive emulsion layers of the present invention with high sensitivity and low sensitivity can also be in the form of not less than two be applied to separate layers. The separate emulsion layers applied in this way with the same spectral sensitivity need not necessarily be arranged adjacent to one another. The separate emulsion layers with the same spectral sensitivity, which have been applied in this way can also have a different sensitivity. This means, when at least one of the blue-sensitive high-sensitivity emulsion layer of the present invention and that of the present invention green-sensitive and red-sensitive emulsion layers in a form of not less than two separate Layers is applied, the layers can be separated from one another, for example as a layer with high sensitivity and as a medium sensitivity layer.

On the side which is closer to the support than the blue-sensitive emulsion layer according to the invention with less Sensitivity can be provided, for example a red-sensitive emulsion layer with low sensitivity UQd with a green-sensitive emulsion layer low sensitivity. In this case it is in the red-sensitive and green-sensitive according to the invention

-AS-

* common emulsion layers expediently to layers with high sensitivity. If the above-mentioned 'red-sensitive and green-sensitive emulsion layers with low sensitivity are provided, the green-sensitive one should Emulsion layer may be arranged in a position farther away from the support than the red-sensitive emulsion layer. The red-sensitive and green-sensitive emulsion layers with low sensitivity can each in the form of not less than two

¹ ^ separate layers are applied in ₇ and in this case the separate layers with the same color sensitivity can have a different sensitivity. That is, if at least one of the red-sensitive and green-sensitive emulsion layers is lower

¹ is applied ^ sensitivity in the form of not less than two separate layers, the layers can be separated, for example, as a layer having a medium sensitivity and a layer of low sensitivity. These separate layers with the same spectral sensitivity need not be adjacent (adjacent).

In the photosensitive material of the present invention, can at each of the interfaces between the respective photosensitive Emulsion layers are non-photosensitive Interlayer may be provided and it is particularly useful to have them between the layers with different spectral sensitivity to be provided. These non-photosensitive Interlayers can contain a cleaning material (removal material).

A yellow filter may be provided, although this is for the present invention is not essential. If necessary, the yellow filter is expediently immediate below the blue-sensitive emulsion layer with high Sensitivity and / or the blue-sensitive emulsion layer arranged with low sensitivity and preferably it is placed on the side facing the wearer

- A 9 -

is closer than the 'blue-sensitive emulsion layer with less Sensitivity.

Below are some examples of the photosensitive Material layer structure of the photosensitive according to the invention Materials indicated, but the invention is in no way limited thereto. The structural component layers are listed below in the order from the sponsoring side:

1) Carrier, red-sensitive, green-sensitive and blue-sensitive Low sensitivity emulsion layers and red-sensitive, green-sensitive and blue-sensitive emulsion layers with high sensitivity;

2) the same structure as specified under (1), but with between the above-mentioned red-sensitive emulsion layers with high sensitivity and the green sensitive emulsion layers with high sensitivity a green sensitivity Medium sensitivity emulsion layer arranged is;

3) the same structure as specified under (1), but with the red-sensitive and green-sensitive emulsion layers with high sensitivity simply by interchanging are in inverted positions;

4) the same structure as specified under (1), but the green-sensitive emulsion layer with low sensitivity is separated into two layers, which consist of a green-sensitive emulsion layer with lower Sensitivity and a green-sensitive emulsion layer with medium sensitivity in the order given viewed from the side closer to the wearer;

5) the same structure as specified under (1), with a lower level between the blue-sensitive emulsion layer Sensitivity and the red-sensitive emulsion layer

-ÄO · -yr-

a red-sensitive emulsion layer with high sensitivity medium sensitivity and a medium sensitivity green sensitive emulsion layer are arranged in the order mentioned from the side which is closer to the wearer;

6) the same structure as specified under (1), with a lower level between the blue-sensitive emulsion layer Sensitivity and the red-sensitive emulsion layer with high sensitivity red-sensitive, green-sensitive and blue-sensitive medium-sensitivity emulsion layers in the order named from which Side viewed from, which is closer to the wearer, are arranged;

7) the same structure as specified under (1), whereby the red-sensitive, green-sensitive and blue-sensitive Emulsion layers with high sensitivity each in two layers are separated, consisting of an emulsion layer of medium sensitivity and one High sensitivity emulsion layer laid in the order named when viewed from the side showing the is closer to the wearer, are arranged;

8) the structure as indicated under (1), whereby the red-sensitive and green-sensitive emulsion layers having high sensitivity are separated into two layers each consisting of a medium sensitivity emulsion layer and an emulsion layer with high sensitivity in the order described, viewed from the side closest to the wearer;

9) the structure as specified under (1), whereby between the blue-sensitive emulsion layer with low sensitivity and the red-sensitive emulsion layer with high sensitivity Sensitivity with a blue-sensitive emulsion layer medium sensitivity is arranged;

10) the structure as indicated under (1), with the red-sensitive and green-sensitive emulsion layers with low sensitivity are each separated into two layers, which consist of an emulsion layer with low sensitivity and an emulsion layer with medium sensitivity in the order described viewed from the side closer to the wearer;

11) the structure as indicated under (1), whereby the red-sensitive, green-sensitive and blue-sensitive Low sensitivity emulsion layers, respectively are separated into two layers consisting of an emulsion layer with low sensitivity and one Medium sensitivity emulsion layer in that described Order, viewed from the side closer to the wearer;

12) the structure as indicated under (1), the red-sensitive emulsion layer having low sensitivity is divided into two separate layers, which consist of a red-sensitive emulsion layer with lower Sensitivity and a red sensitive emulsion layer with medium sensitivity in the order described, viewed from the side that is closer to the wearer.

The above are examples of the photosensitive emulsion layer structure of the photosensitive material of the present invention, but it goes without saying that the photosensitive material of the present invention also includes other constituent component layers such as non-photosensitive ones Intermediate layers, a protective layer, an adhesive layer (subbing layer), an antihalation layer and the like., may have in addition to the emulsion layers specified above.

The grain size of the light-sensitive in the invention

Chen emulsion layers used photosensitive Silver halide grains are not specifically limited to the high emulsion layers However, it is sensitive, for example, to lowering the impairment of the image sharpness of the emulsion layers arranged underneath, the presence of large particles causing light scattering and particles with an average grain size of 0.7 to 2.5 μΐη to be used. It is convenient to granules with an average grain size of 0.5 to 1.5 μπι for the Emulsion layers with medium sensitivity and those with an average grain size of 0.2 to 1.0 μπι for to use the emulsion layers with low (low) sensitivity.

The photosensitive material of the present invention can, though it is not necessarily a cleaning or removal material to inactivate the oxidation product must contain a developer compound, such in its non-photosensitive interlayers and contain other photographic component layers. The cleaning material can be any Type. If it is able to react with the oxidation product of a developing agent in order to inactivate by the oxidation product. To publications in which such cleaners are described, U.S. Patents 2,336,327, 2,360,290, 2,403,721, 2,701,197, 2,710,801, 2,728,659, 3,718,464 and the like. Among the cleaners described in the above publications, in particular those with Advantageously, which are colorless can be used.

For the silver halide which can be used in the present invention, Silver iodobromide and silver bromide are preferred in terms of their high sensitivity, but silver chlorobromide can also be used and silver chloride iodobromide and the like are used will. The effect of the present invention can be obtained by incorporating nothing less

than 50% by weight of the silver halide of a monodispersed silver halide emulsion in at least one of the emulsion layers from the blue-sensitive emulsion layers with low sensitivity to the blue-sensitive emulsion layers with high sensitivity, however, it is desirable that all the emulsion layers of the present invention contain a monodispersed silver halide emulsion in an amount of silver halide of not less contained than 50 wt .-%.

As the monodisperse silver halide (grains) in the present invention, those having a value of not more than 0.20 desired, this value being obtained by taking the standard deviation S of the grain size distribution of the Silver halide grain, as defined by the following formula, divided by the mean grain size r:

_ - ri). ni

S = "

:

■ _f_ < 0.02 and r

particularly preferred - ^ - 0.15

^ ° The mean grain size r used here is in the case of spherical grains by their diameter and in the case of cubic or non-spherical grains Granules around an average of the diameter of the circular images that are obtained when projecting their images can be converted into equivalent circular area images, and each individual grain diameter is the ri and if the number of ri is ni, r is defined by the formula:

Each silver halide grain of the present invention is am most suitably of the core-shell type, and in this case it is preferable that the respective silver halide grains are constructed in such a way that the silver iodide

& content of silver halide in the surface layer (In the case of those of the double core-shell type with two or more shells, the surface layer is to be understood as the outermost shell; the same goes for the next below) does not change significantly. As used herein, "does not matter means that even if the mean grain size changes, the silver iodide content of the surface layer changes does not change significantly and that concretely the difference in the silver halide content between the Surface layers of the granules are preferably not 0.5 mol% exceeds.

Thereby, it is possible to effectively achieve the above-mentioned objects of the present invention, a unified development activity to achieve and to stabilize the chemical ripening of the emulsions. When used according to the invention " of core-shell type silver halide grains, the surface layer appropriately makes no more than 50% and especially not more than 20% of the total weight of the granules. The surface layer comprises expediently silver iodobromide containing no more than 3 mol% silver halide or silver bromide. The core, i.e. the part excluding the surface layer, hereinafter referred to as such, of the silver halide from The core-shell type advantageously contains 0 to 15 mol% iodide. The monodisperse silver halide of the present invention has expediently such a crystal habit that it consists of hexahedral, octahedral or tetradecahedral Crystals.

That in the green-sensitive emulsion layer according to the invention colored magenta couplers contained may be of any type if any

is a compound that can react with the oxidation product of a developer compound to be released a yellow component. The colored magenta coupler used in the green-sensitive emulsion layer of the present invention is contained, can additionally, also in further photographic component layers, including for example a non-photosensitive intermediate layer. When the green-sensitive according to the invention Emulsion layer is applied in the form of not fewer than two layers, at least one of the layers can contain the colored magenta coupler.

The addition amount of the magenta coupler, although not specifically limited, can be 0.05 to 20 mol% and preferably 0.5 to 5 mol%, based on the Silver halide in the emulsion layer to which it is added. The transmission density is albeit there is no specific restriction here either, 0.02

to 0.5, preferably 0.05 to 0.25. 20th

The compounds given below represent colored magenta couplers which can preferably be used according to the invention:

These include, for example, those in the Japanese OPI patent publication 131 448/1974 described compounds of the formula

c-CH

where mean:

R- is an aryl radical or a heterocyclic radical;

R _{2 is} a phenyl radical with a halogen atom, an alkoxy radical or an aryloxy radical in the o-position, based on the imino radical which is connected to a pyrazolone ring in the 3-position; and 5

R, a phenyl radical with a hydroxy radical in the p-position, based on the rest of the Azores. In addition, the compound has a hydrophobic character in its molecule non-diffusible residue. 10

Preferred examples of the compound of the formula I are given on page 3, top right, to page 9, left above of the above patent publication and according to the invention Any of these exemplified compounds can be used, such as 1- (2,4,6-trichlorophenyl) -3- (2-chloro-5-n-tetradecyloxyphenylazo) -2-pyrazolin-5-one and the like

This includes those in the Japanese OPI patent publication 123 625/1974 described compounds of the formula

R,

where mean:

R is a phenyl radical with a substituent;

R ₄ and Rr each represent a hydrogen atom, a halogen atom, a hydroxy radical, an alkyl radical, an alkoxy radical or an acylamino radical, with the proviso that "one of the radicals R _{1 and R 1 represents} a hydroxyl radical and not both radicals R ₄ and R ₅ at the same time denote the hydroxyl radical;

Rg is a hydrogen atom, a halogen atom, an alkyl

-yt-

rest, a nitro radical or an acylamino radical; and

R _{7 is} a hydrogen atom, a halogen atom or a mono-

valent organic residue. 5

Preferred examples of compounds of the formula (II) are given, for example, on page 3, top left, to page 4, bottom left _(of the above-mentioned patent publication. Each of these exemplary compounds can also be used according to the invention and these include, for example:

HO

ι Ι

o == c

NHCOC ₁₅ H ₃₁ (n)

CH ₃

H ₃ CO

ο Il C-CH-

C-CH.

CL

OCH.

_{N == N-} HC C-NH

NHCO (CH ₂ ) 3O

^C 5 ^H ll ^(t)

-νί-

HO

/ ■ \. ^ _H

HO— ^ ~ y-N = N-

C-NH

C-CH.

NHCOCH.

Cl ^.

• N = N-HC-O = C ^ _x .

C-NH

-u KHCOCHO-4 ^ λ-OH

CiI

N = N-HC C-NH

SO:

HO

= N-HC C-NH

Il

C—

'C-CH-

, 1-2)

HO

^C 2 ^H 5

C-NH

SO ₂ NHC ₁₂ H ₂₅ (n)

Cl

BO

-N = N-HC C-NH

HCOCH ₂ O

_{/ 0} H

H.C0-Or-N = N-

\ S //

CZ ^^ k / Cl

-3 Λ

-yf-

HO

_Ν = Ν — HC C — NH

CONHC ₁₀ H ₀₁ - (sec)

H ₃ C

_N == N-HC C-NH

NHCOOC

_12th

OCH-

HO

NHCOC ₅ H ₁₁ (n)

N = N-HC C-NH

I ii

egg.

(16)

OH (η) Η, CC ₇ CONH. - ^ ~ A - N = N - HC C - NH

CH

.32-

-Ά-

HO

HO

N = N-HC C-NH

Cl

NHCHCOOC ₁₂ H ₂₅ (sec)

QL

N = N-HC C-NH

NHcHCOOCH ₉ 2

egg.

C-NH

HCHCONHC ₁₂ H ₂₅ (n)

^C 2 ^H 5

cl

(20)

HO

f /

= N-HC C-NH

NHCH

C /

These include those in the Japanese OPI patent publication 102 723/1977 described 4-phenylazo-2-pyrazolin-5-one compounds, which can be used with advantage, wherein the compounds in the p-position, based on their azo radical, have a substituent alkoxy radical of the formula (III) can have:

wherein Alk is straight or branched chain alkylene radical which can carry an aryl radical substituent, X a connecting radical and Rg an aryl radical or a substituted one Mean aryl radical.

They also include the compounds of the formula described on page 1 of the abovementioned publication

IV

wherein Alk, X and Rg have the meanings given with respect to the formula III; Rg is a hydrogen atom Halogen atom or an electron donating substituent; and Cp a 2-pyrazoline bonded in the 4-position

25 mean 5-one remainder.

In the formula (IV), the radical Cp is expediently a compound of the formula

R, 30

wherein R ₁₀ and R ^ _{1 are} each a known type of substituent in the 2-pyrazolin-5-one coupler used in silver halide color photographic materials.

In addition, the compound of the formula (V) is preferably a compound in which R-. _{Q denotes} an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or a 5- or 6-membered heterocyclic group and R ₁₁ denotes an alkyl group, an acylamino group or an anilino group, each of which may have a substituent.

This also includes the 4-phenylazo-2-pyrazolin-5-one compounds of the formula (VI) given below, in which the 4-phenylazo radical is a substituted alkoxy radical in the p-position, based on its azo radical, which can also be used with advantage:

VI

where mean:

Ro, X and Alk are those given in relation to formula (III) Leftovers;

a phenyl radical or a substituted phenyl radical;

a hydrogen atom, an alkyl radical, an alkoxy radical, a halogen atom, a nitro group, a cyano group or a hydroxyl group;

W is a hydrogen atom, an alkyl group »an alkoxy group, an alkylthio radical, an alkylsulfonyl radical, an aryl radical, an aryloxy radical, an arylsulfonyl radical, an aryloxysulfonyl radical, an amino radical, a substituted amino radical, a carbamoyl radical, a sulfamoyl radical, an N-substituted carbamoyl radical or an N-substituted sulfamoyl radical

amoyl radical.

In addition, compounds of the formulas (III) to (VI.) In which the connecting radical XO, S, CO, SO _2,. SO ₂ O, CONQ, NQCO, SO ₂ NQ or NQSO ₂ denotes, in which Q represents a hydrogen atom, an alkyl radical or an aryl radical.

Preferred examples of compounds of the formulas (III) to (VI) are on page 5, bottom left, up to page 7, at the top right of the above patent publication and any of these exemplary compounds can also can be used according to the invention.

Also usable are compounds represented by the formula (VII) shown below, as disclosed in Japanese OPI Patent Publication 42 121/1977 are:

N — C — R 20

17th

NH — C CH — N = N-

\ ι tr λ

VII

where mean:

R ₁₂ , R ₁ - and R _1. , Which can be the same or different from one another, each represent a hydrogen atom, a halogen atom, a nitro radical, a cyano radical, an alkyl radical, an alkoxy radical, an alkoxycarbonyl radical or a carboxyamido radical;

R ₁₅ represents a hydrogen atom, an alkoxy radical or an aryloxy radical;

R _{16 is} a carboxyamido, a sulfonamido, an alkoxycarboxyamido, an aryloxycarboxy-

V -: - 3410Ü3U

amidorest ,. an aryloxycarboxyamido radical, an imido radical, a carbamoyl radical, a sulfamoyl radical, an alkoxycarbonyl radical or an aryloxycarbonyl radical;

'■ ■ R ₁ - a hydrogen atom or an alkyl radical;

R ₁ O is an alkyl radical, an alkoxy radical, an aryloxy radical, an alkylamino radical or an arylamino _{radical, it being possible for the alkyl radicals represented by R 17} and R _{1ft to} form a cyclic structure

, «• R-cf»

Vco- ''

(4- or 5-membered ring); and

R _{1Q is} a hydrogen atom, a hydroxyl radical, an alkyl radical or an alkoxy radical, with the proviso that when the radical R _- . _{Q is} a hydroxyl radical, the radical in the m ~ position, based on the azo radical, is substituted. In addition, the coupler compound has at least one hydrophobic and nondiffusible group in its molecule.

Preferred examples of compounds of the formula (VII) are on page 6, top right, up to page 10, top on the left of the above patent publication. Each of the compounds given by way of example can also be used according to the invention be used.

Colored magenta couplers which can be used with advantage according to the invention also include those mentioned above such as those disclosed in U.S. Patents 3,519,429 and 2,801,171 and Examined Japanese Patent publication 27 930/1973 are described, and in particular the compounds with the formulas (I), (II), (ΙΙΪ) and (IV), which are in the third and fifth columns of the

-yt-

Letters of U.S. Patent 3,519,429 referenced above, which are most preferred.

Particularly preferred examples among these compounds as described in the above-mentioned patent publications or Descriptions given are the following:

CJL

Cl-

KKCOCHO-

-OH

^C 12 ^H ? 5

OCH.

, K = C-KH

N.

CO-CH CH

N = - N— (/ \ -

\ zZZZf

OH

KHCOC ₁₃ H ₂₇

egg.

<I.

CO-CH

C; V KHCOC:

'CK.

34

_N C-NHCO-Y ^ t " ^C 5 ^H ii

. \ _ / \ · I NHCOCH 0- <7 yt- CH ₁ ,

N == N— (f \ ~ 0CH ₃

Cl

.Qt _M ~ _ _{-NH "i} ^

NHCOC-, ^ H,

N = N- ^ .. ^ —NHCO — C — CH-

CH ₃

, N = C-NH (/ \ CO-

CJi-V > -N 'I ^ = X. /

For the red-sensitive emulsion layer of the invention Ordinary colored cyan couplers can be used. When the red-sensitive emulsion layer of the invention applied in the form of no less than two separate layers is the incorporation of one such colored cyan couplers in the upper layer (further from the support) are desirable with the detergent effect.

As the colored cyan couplers, those described in Japanese Examined Patent Publication can be used 32 46-1 / 1980 and in GB-PS 1 084 480 are described, and the like.

-ar- ·

2> 9-

Particularly preferred cyan couplers are the following compounds:

OH

CONH (CH ₂ ) 4 ° - \ _ V

NaO ₃ S

SO ₃ Na

COOC ₁₆ H ₃₃

OH

CONHC ₁₂ H ₂₅

COOC

The respective photosensitive layers which the invention build up light-sensitive material, their corresponding color-forming couplers (color couplers) contain.

As the yellow color forming couplers (yellow couplers), known open chain ketomethylene type couplers can be used will. Among these couplers, there may be benzoylacetanilide and pivaloylacetanilide type compounds

341063a

can be used to advantage. Examples of such yellow color forming couplers (yellow couplers) are disclosed in US Pat Japanese OPI Patent Publications 26133/1972, 29432/1973, 87650/1975, 17 438/1976 and 102636/1976, in Japanese Examined Patent Publication 19956/1970, in U.S. Pat • 2,875,057, 3,408,194 and 3,519,429 and Japanese Examined Patent Publications 33 410/1976, 10783/1976 and 19031/1971 and the like. Described.

Particularly preferred couplers are as follows:

COCH ₂ CONH

CH.

COOCHCOOC ₁₂ H ₂₅

CH ₀

I ³

CPU — C — COCHCONH

³ I.

cm

° ί

NHCO (CH ₂ J ₃ O

= 0

ct

NHCOCHO

CH -, - C - COCHCONH

CH.

TV N - N

CIL

NHCO (CIL

CH

Qt

CH ₃ —C — COCHCONH

CH

3.

CH.

COOCHCOOC ₁₂ H ₂₅

N - N CiL

CH.

CU

₀ C — COCHCONH-V ^ ^ , Λ = ^

CH.

NHCOCHO

.N.

⁰ T Γ 0 - _: C - CH.

CH.

OCHCONH

OCH

'COCH ₂ CONH

CH ₃ Cl

H-, C-C-COCHCONH

ι ι

CH ₃ Ο

NHCO (CH ₂ J ₃ O

COOH

CH

H-.C-C-COCHCONH

I I

CH 9 S NHCO (CH ₂ ) ₃ 0

OCIL

CH, Ci

I ³

^ C-C-COCHCONH

ι · ι

CH ₃ 0

00Η

LA

^C 2 ^H 5 ^C 15 ^H 31

CH ₃ Ci

CH ₀ -C COCHCONH

~ ³ - ι I CH-,

(η)

CP.

CH ₀ -C COCHCONH

CH ₃

■ N—

N-

NHCO (CH ₂ ) ₃ 0

-CL

Approx.

CH -, - C - COCHCONH 3 ι

CH-

: 4Λ

COOC ₁₆ H ₃₃

⁰ I.

ι
CH.

COCHCONH

N-N 0 CH.

^C 2 ^H 5 -

/ Λ

NHCOCHO

H ₀ OV y-COCHGONH

- ³ \ = / I

N COOC ₁₂ H ₂₅

o = <> = o

JN _n

C ₂ H ₅ O '. ^X CH ₂

(CH ₃ ) ₃ C COCHCONH

Ö NHSO ₂ C ₁₆ H ₃₃ (n)

As a purple color forming coupler (magenta coupler) compounds of the pyrazolone type, compounds of the indazolone type, cyanoacetyl compounds, pyrazolotriazole compounds and the like can be used, and particularly pyrazolone type compounds can be used to advantage will.

Example of a purple one which can be used according to the invention Color forming couplers (magenta couplers) are disclosed in Japanese OPI Patent Publication 111631/1974, Examined Japanese Patent Publication 27930/1973, Japanese OPI Patent Publication 29236/1981, U.S. Patent 2,600,788, 3,062,653, 3,408,194 and 3,519,429, in Japanese OPI Patent Publication 94752/1982 and in Research Disclosure No. 12443 (RD-12443) and the like.

3g Particularly preferred couplers are as follows:

HCOC ₁₃ H ₂₇

.N = C-NHCO

r \

NHCOCH ₂ O

12 "2, NHCOCHO

^C 15 ^H 31

34'IUbJy

Ci-V YN

Ct ^ NC-NH-Q ^ CO-CH-C ₁₈ H ₃₅

ν;

^ CO-CH ₂ ^x C0-CH.

.N = C-NHCO

CJu ^C0 " ^CH 2

1JHC0CH0 C ₂ H ₅

. N = C-NHCOCHO- / J

3W \

N = C-NHCO

/ CO-CH-C ₁₂ H ₂₅

CO-CH

NHCOCHOK / V-OH

N = C-NHCO

NHSO ₂ (CH ₂ )

As a cyan color forming coupler (cyan coupler), there can be used phenyl type compounds, compounds of Naphthol-type and the like can be used and examples thereof are disclosed in U.S. Patents 2,423,730, 2,474,293 and 2,895,826 and US Pat in Japanese OPI Patent Publication 117422/1975 and the like specified.

Particularly preferred couplers are as follows:

H _{1] L} C ₅ -t

(CF ₂ ) ₂ Η

OHCOCHN

OH

¹ Il

OH

CONH (CH ₂ ) ₄ 0

CONH (CH ₂ )

OCH ₉ CONHCH ₂ CH ₂ OCh ₃

OH

C ₅ H ₁₁ -Z] YoCHCONH

.NHCONH

- ^ y-0CHC0NH

The above couplers may contain not less than two of them in combination in the same layer and they can also be contained in no less than two different layers on their own. The training this coupler into the emulsion layers can be carried out by methods known per se. Also according to the invention the above couplers can be incorporated by known methods.

The emulsion layers according to the invention can be non-diffusible Compounds (DIR compounds) that are formed by reacting them with the oxidation product of a developer compound Can release diffusible development inhibitor compounds can be added. As DIR connections For example, such compounds as disclosed in Japanese Patent OPI Publication can be used with advantage 82,424/1977, in U.S. Patents 2,327,554, 3,227,554, and 3,615,506 in Japanese Examined Patent Publication 16 141/1976, in Japanese OPI Patent Publications 145 135/1979 and 151 944/1982 and the like.

Particularly preferred DIR connections are as follows: 30th

- SO-

CH-

CH - C - COCHCONH ι

CH-

Vi ¹¹

HCO (CH ₂ ) ₃ O-fl \ t- <.

H.

N CH

N = C-NH

^C 2 ^H 5

s-cf H

OH

CONH

(η)

ι ι

? 2 ^Η 5

OCHCONH-f V-N

^H 31 ^C 15

N = C-OC ₂ H ₅ S \

CO-CH

N-N

Il τα »ι

/ ^C 18 ^H 35

^C 5 ^H 11

■ NHCO (CH ₂ ) ₃ O

The photographic component layers of the present invention, such as the non-photosensitive interlayers, may contain photographic additives such as anti-discoloration (anti-stain) agents and the like. As the anti-discoloration agent (anti-stain agent), such
Compounds as disclosed in OPI Japanese Patent Publication 2128/1971, U.S. Patent 2,728,659 can be used

and the like, and the following compounds are particularly advantageous:

tC ₈ H ₁₇

^S " ^C 12 ^H 25 ^:

■ ^C 12 ^H 25 ~ ^S

ι OH

'

The one used for the emulsion layers of the invention Silver halide emulsion can be chemically prepared using any of the conventional methods be sensitized. That is, chemical sensitization can be carried out using such sensitizers including active gelatin alone or in combination, such as using Precious metal sensitizers, such as water-soluble gold salts, water-soluble platinum salts, water-soluble palladium salts, water-soluble rhodium salts, water-soluble iridium salts and the like; Sulfur sensitizers; Selenium sensitizers; Reduction sensitizers such as polyamines, stannous chloride and the like; and the like. In addition, the silver halide Be optically sensitized for the desired wavelength ranges by using optical sensitizers either alone or in combination (such as supersensitization) used, which include, for example, cyanine dyes, such as zeromethine dyes, monomethine dyes, Dimethine dyes, trimethine dyes and the like, and merocyanine dyes.

The photosensitive material of the present invention can be used in

the light-sensitive layers and / or other layers (for example in the intermediate layers, in the adhesive layer (Substrate layer), in the filter layers, in the Protective layer, in the image receiving layer and the like.) Various photographic additives contain, depending on for the purposes of these layers, the photographic additives include, for example. Stabilizers or antifoggants, such as azaindenes, triazoles, tetrazoles, imidazolium salts, tetrazolium salts, polyhydroxy

10. compounds and the like; Hardeners, such as compounds of the aldehyde type, aziridine type, isoxazole type, vinyl sulfone type, Acryloyl type, carbodiimide type, maleimide type, methanesulfonate type, Triazine type and the like; Development accelerators such as benzyl alcohol, polyoxyethylene type compounds and the like; Image stabilizers such as chroman, bisphenol and phosphite type compounds; Lubricant, such as wax, glycerides of higher fatty acids, higher alcohol esters of higher fatty acids, and the like; and the like In addition, as a surface-active agent for use as a coating aid, emulsifier, Means for improving the permeability of the treatment or developer liquids into the photosensitive Material, defoaming agent - or material for the control (control) of various physical Properties of the photosensitive material anionic, cationic, nonionic or amphoteric surfactants can be used. As a pickling agent are compounds of the N-guanylhydrazone type, quaternary Onium seed compounds and the like are useful. Alkali salts of the reaction products of p-aminobenzenesulfonic acid are used as antistatic agents with diacetyl cellulose, with a styrene / perfluoroalkyl-sodium maleate copolymer and with a styrene / maleic anhydride copolymer can be used. A vinylpyrrolidone monomer can be used as an anti-color clouding agent containing polymers, a vinyl imidazole monomer containing polymers and the like. Can be used. Methy! Polymethacrylates, polystyrenes, alkali-soluble polymers and the like can be used. aside from that

_:: 0 "6 3

colloidal silica can also be used. As latex to improve physical properties of the layers can be copolymers of acrylic acid esters or V.inyl esters with others containing an ethylene radical Monomers are used. As the gelatin softener, glycerin and glycol type compounds can be used will. A styrene / sodium maleate copolymer, an alkyl vinyl ether / maleic anhydride copolymer and the like. Usable.

The photosensitive material of the present invention is prepared by coating a support with silver halide emulsion layers and other component layers which provide the necessary various photographic Supplements included. Carrier materials that can be used with advantage include, for example, baryta paper, polyethylene-coated paper Paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, polyvinyl acetate, Polypropylene, polyester films such as those made of polyethylene terephthalate, polystyrene and the like. These materials can be arbitrarily selected for use as a support according to the purposes for which the photosensitive is concerned Material is determined.

The carrier made from any of these materials will be the required one Subsequent treatment. ·.

The photosensitive material of the present invention can be according to processed or developed after exposure using a known method, i.e., it can be color developed are made using a commonly used color development process. In the reverse process the photosensitive material is first developed in a developer for black and white negative development and then it is either exposed to white light or treated in a bath containing a fogging agent and then color-developed in an alkaline developing solution containing a color developing agent.

_ ^ 55 - For the development is not particularly limited so that any method may be used, wherein typical examples include a method in which the photosensitive .Material color developed is then bleach-fixed and then washed as required and stabilized; and another method in which the photosensitive material after color development is subjected to separate "fixing and bleaching processes, and if necessary washed and then stabilized. A method for photosensitive materials in which an enhancer such as hydrogen peroxide, cobalt complex salts or the like is used , are also known, and these methods can also be applied to the processing of the light-sensitive material of the present invention, There are cases where these processing is carried out at a high temperature to be carried out quickly or at room temperature or, in a special case, at a temperature below room temperature. In performing high-temperature rapid development, a pre-hardening treatment can also be applied. There are also cases where auxiliary baths such as various neutralizing agents Baths, become necessary depending on the kind of treatment or developing chemicals used, so that these auxiliary baths can be selected as necessary.

Useful color developing agents are primary phenylenediamines and derivatives thereof and typical examples include 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N-ethyl-N-ß-hydroxyethyl-N-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-ß-methanesulfonamidoethylaniline, 3 ~ methyl-4-amino-N-ethyl-N-ß-methoxyethylaniline, 3-ß-methanesulfonamidoethyl-4-amino-N, N-diethylaniline, 3-methoxy-4-amino-N-ethyl-N-ß-hydroxyethylaniline, 3-methoxy-4-amino-N ~ -ethyl ~ N-ß-methoxyethylaniline, 3-acetamido-4-amino-N, N-diethylaniline, 4-amino-N, N-dimethylaniline, N-Ethyl-N-ß ~ / j} - (ß-methoxyethoxy) ethoxyjethy1-3-methyl-

4-aminoaniline, N-ethyl-N-ß- (ß-methoxy) ethyl-3-methyl-4-arainoaniline and salts of these compounds, such as the sulfates, hydrochlorides, sulfites, p-toluenesulfonates and the like.
5

With the present invention it is not only possible to achieve the above objects of the invention, but it is also possible without using any yellow filters To achieve effects similar to those in the cases in which yellow filters are provided, so that the present Invention provides a photosensitive material which, despite its high sensitivity, has the potential to occur of a haze ", has less color haze and is excellent in heat resistance.

.

The invention is illustrated in more detail by the examples described below, but without being restricted thereto be. -, ·

Examples

First, the method of manufacture that is included in the Emulsions used in the examples described below are described.

Preparation of a polydisperse emulsion

An aqueous silver nitrate solution and an aqueous alkali halide solution were spontaneously dropped into a reaction vessel which was previously an aqueous gelatin solution and an excessive amount of a halide, and then an aqueous Demol solution (a product from Kawo Atlas Co.) and an aqueous magnesium sulfate solution were added to precipitate a precipitate was then desalted, and gelatin was added thereto to produce an emulsion having a pAg value of 7.8 and obtained a pH of 6.0. The resulting emulsion was prepared using sodium thiosulfate, chloroauric acid and ammonium rhodanate and then added 4-hydroxy-6-methyl-1,3,3a, 7-

-M-

tetrazainden and S-nitrobenzimidazole as well as gelatine added, whereby a polydisperse silver iodobromide emulsion was obtained. In this procedure, the mole percentage of silver yodide varies by changing the alkali halide composition and the mean particle size and the particle size distribution were varied by change the addition times of the silver nitrate solution and the alkali halide solution.

Preparation of a monodisperse emulsion

To the seed grains of a silver halide and an aqueous gelatin solution previously placed in a reaction vessel were introduced, under the control of the pAg value and the pH value thereof, an ammoniacal one Silver nitrate solution and an aqueous potassium iodide solution as well. Potassium bromide solutions in proportional amounts according to the increasing surface area of the growing Granules added. An aqueous Demol solution (a product of Kawo Atlas Co.) was then added to the emulsion. and an aqueous magnesium sulfate solution was added to thereby precipitate a precipitate, which was then desalted and "gelatin was added thereto for preparation an emulsion with a pAg of 7.8 and a pH of 6.0. Sodium thio- · sulfate, chloro-gold (III) acid and ammonium rhodanate added, to let them ripen chemically, and also 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 6-nitrobenzimidazole and gelatin added for production a monodisperse silver iodobromide emulsion .. At this procedure was the mole percentage of silver iodide by 'changing the ratio between' the amounts of Potassium iodide and potassium bromide varies and the particle size was varied by changing the addition amounts of ammoniacal silver nitrate and potassium halides and the crystal habit of the silver halide particles became varies by changing the pAg value during the reaction.

In addition, a core / shell emulsion was based on the Japanese OPI patent publication 48521/1979 manufactured.

Example 1 '. · '. ·

The layers shown below were applied in the order listed on a transparent substrate made of a subbed cellulose triacetate film, the reverse side of which was coated with an antihalation layer (the antihalation layer contained 0.40 g of black colloidal silver and 3.0 g of gelatin) for preparation a sample 1. · In addition, in all of the following examples the amounts added to the light-sensitive material per m ² are given, with the exception of those of the silver halide emulsion and the colloidal silver, which are given in silver equivalents. -. -

Sample 1 - Comparative Example

■ 20 '. "■' .-...

Layer 1; A red-sensitive silver halide emulsion layer of low sensitivity, containing a red-sensitive silver iodobromide emulsion ^ low sensitivity, 2.2 g of gelatin and 0.8 g of tricresyl phosphate (TCP), which is used to dissolve 1.0 g of 1-hydroxy-4- (β- methoxyethyl ~ aminocarbonylmethoxy) -N - * ^ £ - (2 ^ -di-t-'amylphenoxyibutylj- ■ 2-naphthoamide (hereinafter referred to as "cyan ^{coupler 11} - .. net), 0.075 g disodium-1-hydroxy-4- / 4- (1-hydroxy-S ~ acetamido-3, 6-di-sulfo ~ 2-naphthylazo) phenoxy7-N-22> - (2, 4-di-t-amylphenoxy) butyl-2-naphthoamide (hereinafter referred to as " colored cyan coupler) and 0.01 g of 1-hydroxy ~ 2- / 2v- (2,4-di-t-amylphenoxy) -n-butyl7naphthoamide, 0.07 g of 2-bromo-4- (2.2, 3,3,4,4,5,5,6,6,7 / 7 _i 8,8,9,9-hexadecafluorononanoylamino) -7-nitro-2- (1-phenyl-5-tetra.zolylthio) -1 indanone (hereinafter referred to as "DIR compound") was used.

Layer 2: an intermediate layer containing 0.07 g of 2,5-dit-octy! Hydroquinone (hereinafter referred to as "anti-discoloration agent") dissolved in 0.04 g of n-dibutyl phthalate (hereinafter referred to as "DBP ¹¹ "), and 0.8 g gelatin.

Layer, 3; A low-sensitivity green-sensitive emulsion layer containing 1.40 g of green-sensitive low-sensitivity silver iodobromide emulsion, 2.2 g of gelatin and 0.95 g. TCP, in which 0.8 g of 1- (2,4,6-trichlorophenyl) -3- / 3- (2 ^ -di-t-amylphenoxyacetamidojbenz-

amidq7-5-pyrazolone (hereinafter referred to as "magenta coupler" '), 0.15 g of 1- (2,4,6-trichlorophenyl) -4- (1-naphthylazo) -3 - ^ - chloro-S-octadecenylsuccinimidoaniline) -5-pyrazolone (hereinafter referred to as "colored magenta coupler") and 0.012 g of DIR ^ compound.

Layer 4: The same layer as Layer 2.

Layer 5: A red-sensitive high-sensitivity emulsion layer containing 1.5 g of red-sensitive high-sensitivity silver iodobromide emulsion, 1.2 g of gelatin, and 0.30 g of TCP in which 0.26 g of cyan coupler and 0.03 g of colored one were dissolved Cyan coupler.

Layer 6: The same layer as Layer 2.

Layer 7: A green-sensitive high-sensitivity emulsion layer containing 1.6 g of green-sensitive high-sensitivity silver iodobromide emulsion, 1.9 g of gelatin and 0.25 g of TCP in which were dissolved 0.20 g of magenta coupler and 0.049 g of colored magenta coupler.

Layer 8; A yellow filter sheet containing 0.15 g of yellow colloidal silver, 0.2 g of anti-discoloration agent dissolved in 0.11 g of DBP, and 1.5 g of gelatin.

Layer 9: One blue-sensitive emulsion layer less

- ·; ■; ··. ■: ■ -. ; 34iO63y

GO -

Sensitivity containing 0.5 g of blue-sensitive silver iodobromide emulsion low sensitivity, 1.9 g gelatin and 0.6 g TCP, in which 1.5 g of t <-pivaloyl-sX- (1 -benzyl-2-phenyl-3, 5-dioxoimidazolidin-4-yl) 2 '-chloro-5' - / öc-dodecyloxycarbonyl) ethoxycarbonyljacetanilide (hereinafter referred to as "yellow coupler").

Layer 10: A blue-sensitive high-sensitivity emulsion layer containing 0.8 g of blue-sensitive high-sensitivity silver bromide emulsion, 1.5 g of gelatin and 0.65 g of TCP in which 1.30 g of yellow coupler was dissolved.

Layer 11: A protective layer containing 2.3 g of gelatin.

In the same way as Sample 1 above, 'also Samples 2 to 10 were made as follows. In the following information, the expressions "above layer 1, above layer 2 ... above layer 11 "for the respective εσΙιίσΐΊ ^ ημίηΐηεΓη in rehearsal 1..

Sample 2, - Comparative Example '. .

Layer 1: The same layer as Layer 1 above

Layer 2: The same layer as Layer 5 above

Layer 3: The same layer as the above layer .4

Layer 4: The same layer as Layer 9 above

Layer 5: The same layer as Layer 4 above

Layer .6: The same layer as Layer-3 above

Layer 7: The same layer as Layer 7 above

Layer 8: The same layer as Layer 8 above

Layer 9: The same layer as the above layer

Layer 10: The same layer as the above layer. 11

Sample 3 - Comparative Example
35

Layers T. - 4: The same as Layers 1 above

to 4 of sample 1

Layer 5: The same layer as Layer 9 above Layer 6: The same layer as Layer 4 above

Layer 7: The same layer as Layer 5 above

Layer 8: The same layer as Layer 4 above

Layer 9: The same layer as the above layer

Layer 1.0: The same layer as Layer 4 above

Layer 11: The same layer as the above layer

Layer 12: The same layer as the above layer

Sample 4 - Comparative Example

Sample 4 was made in the same manner as Sample 3 produced, but with the exception that from the emulsion layer, layer 9 of sample 3, the colored magenta coupler removed · and that the polydisperse silver halide grains were replaced by monodisperse silver iodobromide grains (distribution 12%, mean grain size 3.4 μm).

Sample 5 - example according to the invention

■ Sample 5 was made in the same manner as. the sample 3 prepared, but with the exception that the same monodisperse Silver halide grains as in Sample 4. put the silver halide particles of the emulsion layer as Layer 9 der.Probe 3 were used.

Sample 6 - inventive example

Sample 6 was made in the same manner as Sample 5 produced, but with the exception that only 70% of the silver halide of the emulsion layer, layer 9 of the Sample 5 was replaced with monodisperse silver halide grains.

Sample '7 - inventive example

Sample 7 was manufactured in the same manner as Sample 5 except that the items the layer 7 and the layer 9 of the sample 5 were exchanged.

Sample 8 - example according to the invention

Sample 8 was made in the same manner as Sample 5 produced, but with the exception that the positions of layer 1 and layer 3 of sample 5 are interchanged became. '. ■ '

Sample 9 - inventive example

Sample 9 was made in the same manner as Sample 5 except that the silver halide grains. of all the emulsion layers of the layer 7, the layer 9 and the layer 11 of the sample 5 by the same monodisperse silver halide particles as in the layer. 9 of Sample 4 were replaced and that the silver halide particles the layer 5 also by monodisperse silver halide ■ genid granules (distribution 10%, mean particle size 0.8 μΐη) were replaced.

Sample 10 - inventive example _ '

Sample 10 was made in the same manner as Sample 9 with the exception that the monodisperse silver halide emulsion of layer 7, layer 9 and the layer i1 and the monodisperse silver halide emulsion of the layer 5 of the sample 9 all through. a core / shell- ' Silver halide emulsion were replaced. . '

Each of the samples produced was then optically viewed Step wedge (gray wedge) exposed to neutral light and separate exposures were made, corresponding to the Neutral light exposure was carried out and then they were made using the procedures described below developed to obtain dye images. The properties obtained are as follows Given in the table. .

* Treatment stages (at 38 ⁰ C) treatment duration

Color development 3 min and 15 s

Bleaching 6 min and 30 s

Wash '3 min and 15s

Fix for 6 min and 30 s

Washing 3 min and 15 s

Stabilize for 1 min and dry for 30 s

The compositions of the ver The following treatment fluids were used:

Color developer

4-Amino-3-methyl-N-ethyl-N ~ (β-hydroxyethyl) aniline sulfate

anhydrous sodium sulfite hydroxylamine hemisulfate. anhydrous potassium carbonate sodium bromide

Trisodium nitrilotriacetate monohydrate potassium hydroxide
Water ad

Bleach bath

Iron ammonium ethylenediaminetetraacetate 100.0 g

Diammonium ethylenediaminetetraacetate - 10 · ', 0 g

Ammonium bromide. · 150, ο g

Glacial acetic acid 10.0 ml

Water ad 1 1 aqueous ammonia to adjust the pH. 6.0

Fixer · ·

Ammonium thiosulfate x 175.0 g

anhydrous sodium sulfite - 8.6 g

Sodium metabisulfite 2.3 g

Water _ . ad 1 1

Acetic acid to adjust the pH to 6.0

4.75 G 4.25 G 2.0 G 37.5 G 1.3 G 2.5 G 1.0 G 1 1

Stabilizing bath

Formalin (aqueous. 37% solution)

Koniducks (a product of Konishiroku Photo Ind. Co., Ltd.)

Water ad

1.5 ml

7.5 ml 1 1

Tabel

"""""^ -—- ^^^ Sample No.
achieved EigSn —- ^. relative discovery
! .ioViV-pit 1 2 3 4th 5 6th 7th 8th 9 10 B. MTF ³⁾ ■ 100 102 101 107 105 105 106 107 130 132 G RMS ⁴⁾ 68 65 66 71 70 68 67 71 75 77 HE ² ) 68 69 65 63 57 58 56 56 55 54 R. relative sensibility 0.01 0.06 0.08 0.09 0.09 0.09 0.09 0.09 0.10 0.10 MTF 100 105 118 121 167 159 158 166 176 187 RMS 40 47 40 44 54 51 52 52 54 57 . HE ' 43 41 45 43 36 38 36 35 32 32 relative encpf ind-
opportunity 0.03 0.02 0.06 0.08 0.09 0.08 0.09 0.10 0.10 0.10 MTF 100 82 118 111 128 123 128 129 180 192 RMS 33 32 33 36 39 38 38 38- 43 46 HE. 48 47 48 48 44 44 43 ' 44 ..42 40 ·· 0.03 0.02 0.09 0.10 0.10 0.10 0.10 0.10 0.10 0.10

In the table above, B, G and R denote the measured relative values for blue, green and red light.

The sensitivity of each sample is shown in the table as relative sensitivity, related to the sensitivity of Sample 1, which was set at 100.

The interframe effect (IIE) is indicated, expressed

by the degree of increase in Alog E (E = exposure) - ' Sensitivity determined at a D. "+0.3 density point of the dye image of each sample obtained when subjected to the separate exposures (separate red, green and blue light exposures corresponding to the total amount of neutral exposure),

, _ matched that of the same sample received Io

when this was the neutral exposure (red + green + Blue exposure).

The determination of the improvement effect in relation to the Image sharpness was achieved by finding out the MTF (modulation transfer function) of each sample and then comparing the size of the MTF in the spatial frequency of 30 Lines / mm between samples.

' The RMS is given as 1000 times the value of the standard

standard deviation of the D. + 0.8 density of each sample, the · ^ mm ^J

was determined when their dye image through the circular Scanning head of a microdensitometer with a diameter of 2 5 μΐη was scanned.

As can be seen from the table above, an increase in sensitivity can be achieved by using the Layer structure of the present invention (as in Samples 3 through 10, compare with Samples 1 and 2). The single ones Effects of the monodisperse emulsion alone (Sample 4) and the colored magenta coupler alone (Sample 3) are not noticeable, but when they are used in combination, especially the green sensitivity becomes strong increased and the effect is very clear when

3 4 Ί U b 3 U

all emulsion layers according to the invention from the monodisperse Emulsion exist as in sample 9, and also the effect is greatest when the monodisperse emulsion of the core / shell type as used in Example 10. Also point in terms of improving graininess the samples according to the invention have a far lower RMS than that in the monodisperse emulsion containing alone Sample 4 and Sample 3 containing the colored magenta coupler alone; i.e., the inventive Samples show a greatly improved graininess. It was also found that through additional Using the monodispefsen emulsion the transmission up to the lower layer was increased significantly, whereby the sharpness of the image was increased, and this effect was surprising in view of the single effect of using them separately clear. It can also be seen from this that the inter-image effect has also been greatly improved.

Claims (26)

T 54 431 Applicant: Konishiroku Photo Industry Co., Ltd. No. 26-2 Nishishinjuku 1-chome Shinjuku-ku Tokyo / Japan claims 1. silver halide color photographic photosensitive material, I denote it by a carrier on which at least one green-sensitive one is applied Silver halide emulsion layer, at least one red-sensitive silver halide emulsion layer and a variety of blue sensitive silver halide emulsion layers with different sensitivity, one of the plurality of blue-sensitive silver halide emulsion layers is provided as the silver halide emulsion layer furthest from the support; that between the most distant blue-sensitive Silver halide emulsion layer and the other blue-sensitive silver halide emulsion layer with a smaller one Sensitivity than the most distant blue sensitive Silver halide emulsion layer at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer are provided; that at least one silver halide emulsion layer of the emulsion layers consisting of the two blue-sensitive Silver halide emulsion layers and the green-sensitive silver halide emulsion layer and the red " sensitive silver halide emulsion layer between the two blue-sensitive silver halide emulsions layers are arranged, monodisperse silver halide * contains small grains; and that between the two blue-sensitive silver halide emulsion layers provided at least one green-sensitive silver halide emulsion layer a Contains colored purple coupler. 2. Silver halide color photographic light-sensitive material according to claim 1, characterized in that it is the monodisperse silver halide grains containing layer around a blue-sensitive emulsion layer having high sensitivity or a green-sensitive one High sensitivity emulsion layer. 3. Silver halide color photographic light-sensitive material according to claim 1 or 2, characterized in that all light-sensitive emulsion layers which Build up light-sensitive material, monodisperse silver halide grains contain. 4. Silver halide color photographic light-sensitive material according to any one of claims 1 to 3, characterized in that the monodisperse silver halide grains are is of a core-shell type. 5. Light-sensitive silver halide color photographic material according to one of claims 1 to 4, characterized in that the layer structure of the light-sensitive Materials include red-sensitive, green-sensitive and blue-sensitive emulsion layers with less Sensitivity in the order listed by the wearer calculated from, and that red-sensitive, green-sensitive ones are also arranged on these emulsion layers and blue-sensitive emulsion layers with high sensitivity in that order. 6. Silver halide color photographic light-sensitive material according to claim 5, characterized in that the difference in sensitivity between the emulsion high sensitivity layers and the emulsion layers with low sensitivity is 0.3 to 0.6 logE. 7. The light-sensitive silver halide color photographic material according to claim 5 or 6, characterized in that the emulsion layer with high sensitivity and the emulsion layer with low sensitivity have substantially the same spectral sensitivity and
that the two emulsion layers mentioned have a photographic non-diffusible after color development
Contain coupler capable of forming a dye with substantially the same hue. 8. Silver halide color photographic light-sensitive material according to one of claims 1 to 7, characterized in that at least one layer each of the red-sensitive emulsion layers and the green-sensitive Emulsion layers between the emulsion layer with less Sensitivity and the emulsion layer with high Sensitivity of the blue-sensitive emulsion layers
is arranged and that the green-sensitive Emulsions.-layer is arranged further away from the carrier than
the red sensitive emulsion layer. 9. Light-sensitive color photographic silver halide material according to any one of claims 5 to 8, characterized in that the mean particle size in the
photosensitive emulsion layer in photosensitive silver halide grains used with high sensitivity 30chen is 0.7 to 2.5 μm and that their mean particle size in the light-sensitive emulsion layers with low sensitivity is 0.2 to 1.0 μΐη. 10. Silver halide color photographic light-sensitive material according to one of claims 3 to 9, characterized characterized in that all of the emulsion layers comprise a monodisperse silver halide emulsion in an amount of silver halide of contain not less than 50% by weight. 11. Silver halide color photographic light-sensitive material according to any one of claims 1 to 10, characterized in that the monodisperse silver halide grains each have a value not more than 0.20, which value is calculated by dividing the standard deviation S is the grain size distribution of the silver halide grain defined by the formula given below, through the mean grain size r: * fa - ri> ² ni ² g -: where, under the term "mean grain size r" as used herein, in the case of spherical grains, their diameter and in the case of cubic or non-spherical grains, an average value of the diameters of circular images is to be understood which is obtained when their projection images are converted into equivalents circular surface images are converted, and each individual grain diameter is denoted by ri and then, if the number of r is ni, the r is defined by the formula: __ v? ni ri ^{r =} 12. Silver halide color photographic light-sensitive material according to any one of claims 4 to 11, characterized in that each of the silver halide grains is built up so that the silver iodide content of the SiI overhalide does not change significantly on the surface layer. 13. Silver halide color photographic light-sensitive material according to one of claims 4 to 12, characterized in that the surface layer is not more than Makes up 50% of the total weight of the granules. * 14. Silver halide color photographic light-sensitive material according to one of claims 4 to 13, characterized / that the surface layer comprises silver iodobromide, which does not contain more than 3 mol% silver iodide, 5 or silver bromide and that the core of the silver halide from "core-shell type 0 to Contains 15 mol% silver iodide. 15Γ Photosensitive 'color photographic silver halide material according to any one of claims 1 to 14, characterized in ¹ ^ that the monodisperse silver halide having a crystal habit such that the crystal is a hexahedral, octahedral or tetradecahedral crystal. 16. Silver halide color photographic light-sensitive material according to one of claims 1 to 15, characterized in that the content of the colored magenta coupler, which is contained in at least one of the green-sensitive emulsion layers, 0.5 to 5 mol%, based on on the silver halide. 17. Silver halide color photographic light-sensitive material according to one of claims 1 to 16, characterized in that the transmission density of the colored Magenta coupler contained in at least one of the green-sensitive silver halide emulsion layers, Is 0.05 to 0.25. 18. Silver halide color photographic light-sensitive material according to one of claims 1 to 17, characterized in that it is the colored magenta coupler is a compound of the general formula: N Ln * ³ <*> -δι where mean: R _{1 is} an aryl radical or a heterocyclic radical; R _{2 is} a phenyl radical with a halogen atom, an alkoxy radical or an aryloxy radical in the o-position, based on den'Iminorest, which is in the 3-position linked to a pyrazolone ring; and R _{3 is} a phenyl radical with a hydroxy radical in the p-position, based on the azo radical. 19. Silver halide color photographic light-sensitive material according to one of claims 1 to 18, characterized in that it is the colored magenta coupler is a compound of the general formula R. where mean: R is a phenyl radical with a substituent; R. and R ₅ each represent a hydrogen atom, a halogen atom, a hydroxy radical, an alkyl radical, an alkoxy radical or an acylamino radical, with the proviso that one of the radicals R. and R _{5 is} a hydroxy radical and not both radicals R and Rc are simultaneously hydroxy radicals could be; R _{6 represents} a hydrogen atom, a halogen atom, an alkyl radical, an alkoxy radical, a nitro radical or an acylamino radical; and R _{7 is} a hydrogen atom, a halogen atom or a monovalent organic radical. 20. Silver halide color photographic light-sensitive material according to one of claims 1 to 19, characterized in that the colored purple-red coupler is a 4-phenylazo-2-pyrazolin-5-one compound which is in the p-position, based on its azo radical, has a substituent alkoxy radical of the formula -0-AIk-X-Ji ₀ (HD where mean: Alk is a straight-chain or branched-chain alkylene radical, which can carry an aryl radical substituent; X is a linking group; and Rg is an aryl radical or a substituted aryl radical. 21. Silver halide color photographic light-sensitive material according to claim 20, characterized in that the colored magenta coupler is a Compound of formula acts * -Afr-y- * ^(IV) V = / ^ S wherein Alk, X and Rg have the same meanings as in the formula (III), R _g is a hydrogen atom, a halogen atom or an electron-donating substituent, and Cp represents a 2-pyrazolin-5-one radical, which in the 4-position is bound. 22. Silver halide color photographic light-sensitive material according to claim 21, characterized in that the radical Cp in the formula (IV) is a Compound of formula acts N
35 where mean: R _{1n is} an alkyl radical, a substituted alkyl radical, an aryl radical, a substituted aryl radical or a 5- or 6-membered heterocyclic radical; and R _{11 is} an alkyl group, an acylamino group or an anilino group. 23. Silver halide color photographic light-sensitive material according to one of claims 20 to 22, characterized in that it is the colored magenta coupler is a 4-phenylazo-2-pyrazolin-5-one compound of the formula (VI) given below, wherein the 4-phenylazo radical is a substituted alkoxy radical in the p-position, based on their azo residue, has: O = C N Z n = N-CH-C-NH where mean: Rg, X and Alk are the same radicals as in the formula (III); Y is a phenyl radical or a substituted phenyl • rest; Z represents a hydrogen atom, an alkyl radical, an alkoxy radical, a halogen atom, a nitro group, a cyano group or a hydroxyl radical; W is a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an aryl radical, an aryloxy radical, an arylsulfonyl radical, an aryloxysulfonyl radical, an amino radical, a substituted amino radical, a carbamoyl radical, a sulfamoyl radical, an N-substituted carbamoyl radical or an N-substituted sulfamoyl radical. 24. Silver halide color photographic light-sensitive material according to claim 20, 21 or 23, characterized indicates that the bonding radical X is selected from O, S, CO, SO ₀ , SO ₀ O, CONQ, NQCO, SO ₀ NQ or NQSO ₀ , in which Q represents a hydrogen atom, an alkyl radical or an aryl radical.
5 25. Silver halide color photographic light-sensitive material according to one of claims 1 to 24, characterized in that that the colored magenta coupler is a compound of the formula 10 where mean: ^R 12 ' ^R 13 ^unc ^ ^R 14' ^ ^B 9l ^e i ° h or different from one another, in each case a hydrogen atom, a halogen atom, a nitro radical, a cyano radical, an alkyl radical, an alkoxy radical, an alkoxycarbonyl radical or a carboxyamido radical; R _{15 is} a halogen atom, an alkoxy group or an aryloxy group; R- r a carboxyamido radical, a sulfonamido radical, an alkoxycarboxyamido radical, an aryloxycarboxyamido radical, an imido radical, a carbamoyl radical, a sulfamoyl radical, an alkoxycarbonyl radical or an aryloxycarbonyl radical; R ^ - a hydrogen atom or an alkyl radical; R.jg an alkyl radical, an alkoxy radical, an aryloxy radical, an alkylamino radical or an arylamino radical, where the alkyl represented _{by R 1} ^ and R ₁₀ I / Io residues can form a 4- or 5-membered ring; and 26. Silver halide color photographic light-sensitive material according to one of claims 1 to 25, characterized in that it is the colored magenta coupler is a compound of the formula: 4 R ₆ R.
R ₅ ^ Ca-N = N-HC C-NH-C - ^ 1 ii I O = C ^ N ^ R "(VIII) where mean:
R is a phenyl radical with a substituent; R ₄ and R ₅ each represent a hydrogen atom, a halogen atom, a hydroxy radical, an alkyl radical, an alkoxy radical or an acylamino radical, with the proviso that one of the radicals R ₄ and R _{5 represents} a hydroxyl radical and not both radicals R ₄ and R ₅ at the same time Can be hydroxyl radicals; R _{6 represents} a hydrogen atom, a halogen atom, an alkyl radical, an alkoxy radical, a nitro radical or an acylamino radical; and R _{7 is} a hydrogen atom, a halogen atom or a monovalent organic radical.