DE3321630A1 - LIGHT SENSITIVE PHOTOGRAPHIC SILVER HALOGENIDE MATERIAL - Google Patents

Description

T 54 050

Applicant: Konishiroku Photo Industry Co., Ltd.

No. 26-2 Nishishinjuku 1-chome Shinjuku-ku

Tokyo / Japan

Silver halide photographic light-sensitive material

This invention relates to a silver halide photographic light sensitive material, and particularly relates to it a silver halide photographic light-sensitive material exhibiting satisfactory photographic properties, in particular gives excellent contrast, both when it is in a developer liquid from the Lith type as well as in a developing liquid of the non-lith type is treated or developed.

Silver halide photographic light sensitive materials are generally used within a very wide range of applications because their photographic Easily adjustable sensitivity, gradation and the like are.

So it is particularly necessary in the lithographic field to have a photosensitive material with a very

gO to use high contrast, so so far it has been general The practice was to employ a method in which, as a separate method, a light-sensitive photographic Silver halide material containing a relatively large amount of silver chloride is used, which in one Developer is treated or developed with a relatively low sulfite concentration, which in principle contains a dihydroxybenzene-type compound (hereinafter referred to as a lith-type developer),

3 3 21 6 3 W.

in order to create an image made from halftone! ' points and lines with an extremely high contrast,

_.-: ** "stands. J

&"* 5 When the silver halide emulsion layer of the above ί k;

described photosensitive photographic silver <>> \

k ' halide material contains a compound which in its m

% '■' ^fi M

λ '\'. Molecule contains a polyalkylene oxide chain, such as example ^

As described in Japanese Examined Patent Publication '' f '10 25 201/1967 and Japanese Patent Laid-Open Publication (hereinafter referred to as Japanese OPI Patent Publication) No. 108 130/1977, the image becomes even more contrasty, so that the image quality is greatly improved.

15th

As a photosensitive material for application on the graphic field where high contrast of the image is required is a satisfactory one physical properties such as satisfactory dimensional stability, adhesion of the layer the wearer, adaptability to the treatment or development required in an automatic developer and the like. In order to meet these requirements, it must light-sensitive material must be constructed so that the amount of gelatin used therein is as small as possible.

However, the image quality improving effect obtained by the above-mentioned polyalkylene oxide type compound depends largely on the amount of gelatin used.

When the amount of gelatin is small, the effect also becomes rather small, so that to improve the Effect the compound must be added in a considerable amount, in some cases the required amount Amount must even be up to several grams per mole of silver halide.

As a treatment or development liquid for a light-sensitive silver halide material with one of the

- & -

On the other hand, a developer liquid of the non-lith type is often used for high contrast, which, although hardly able to produce an image as high in contrast as the lith-type developer ° provide a relatively large amount of a sulfite to stabilize them and a developing agent which is not limited to a dihydroxybenzene-type compound (this combination becomes more general applied; the lith type developer liquid is rather considered special), but if the photosensitive one Material containing a large amount of the above-mentioned alkylene oxide type compound in one Developer of this type is treated or developed, the image contrast of the light-sensitive material decreases

! 5 clearly decreases with increasing veil, so that no good ones photographic properties can be achieved.

The aim of the present invention is therefore to provide a photosensitive to provide silver halide photographic material which gives satisfactory contrast can, both when in a lith-type developer liquid and in a non-lith-type developer liquid is treated or developed. Another object of the invention is to provide a photosensitive photographic To provide silver halide material capable of producing an image with excellent contrast without affecting the photographic speed and fog thereof. Further Objects, features and advantages of the invention will become apparent from the following description of the invention and from the further examples described below.

According to the present invention, the above objects can be achieved with a photosensitive photographic A silver halide material which has on its support at least one layer which contains (1) silver halide grains, which contain at least 50 mol% silver chloride, (2) a liquid paraffin or finely divided solid

Paraffin with an average particle size of not more than 5 μm and (3), a compound found in has an alkylene oxide chain in its molecule.

The present invention is characterized in that that the photographic component layer of a photosensitive Superhalide photographic material for lithographic use is a liquid or solid paraffin and a polyalkylene oxide type compound are incorporated, thereby making a photosensitive silver halide photographic material having excellent photographic properties and an extreme high contrast can be obtained, which was previously not possible with the conventional methods.

Preferred compounds which can be used according to the invention in combination with liquid or solid paraffin and contained in the above photographic component layer and a polyalkylene oxide chain in its molecule are those that preferably have one of the following general formulas:

R ₁ O (CH ₂ CH ₂ O) Im (CH ₂ CHO) Pi (R ₂ O) H ₁ (CH ₂ CHO) P ₂ (CH ₂ CH ₂ O) In ₂ R _{3 (I)}

CH ₂ Rm. CH ₂ Rh

₃ (CH ₂ CH ₂ CH ₂ CH ₂ O) P ₃ (R ₂ 0) n ₂ (CH ₂ CH ₂ CH ₂ CH ₂ O) P ₄ and RyO (R ₂ OJn ₃ (CH ₂ CH ₂ O) m ₅ Rs (III)

wherein mean;

R-, * R-3 / Rr; Rg ι R ₇ and Rg each hydrogen, a substituted or unsubstituted alkyl, aryl or acyl radical,

R ₂ -CH ₂ CH- or -CH ₂ CH ₂ CHaCH ₂ -; CH ₂ R?

R ₄ and R each hydrogen, an alkyl or cycloalkyl radical with 1 to 4 carbon atoms or an alkoxy or aryloxy radical with 1 to 8 carbon atoms, n .., n ₂ and n ₃ each an integer of up to 5, P ₁ ⁺ P-. ' Ρτ + p, each an integer from 0 to 60, before-

1 preferably from 0 to 30, and

m.j + m ₂ , rru + m. and In ₅ each is an integer from 10 to

Below are some typical examples of compounds of the above formulas to which however, the invention is by no means limited.

-JS-

Exemplary connections

CH.

(2) HO (CH ₂ CH ₂ O) To (CH ₂ CHO) ρ

CH ₃

(m + η = 19 P = 21)

nH

(m + n = 31 P = 35)

(3) HO-C-CH ₀ CH ₀ CO- (CH ₀ CH ₀ O) η (CH ₀ CHO) ρ (CH ₀ CH ₀ O) n C-CH _o CH _o -C-0H

CH.

(m + n = 16 p = 17)

(4) HO (CH ₂ CH ₂ O) πι (CH ₂ CHO) PiCH ₂ CHO (CH ₂ CHO) ρ ₂ (CH ₂ CH ₂ O) ηΗ

(m + η = 24 P ₁ + ρ ₂ = 12)

(5) HO {CH ₂ CH ₂ O) m (CH ₂ CHO) P ₁ Ch ₂ CHOCCH ₂ CHO) ₂ P (CH ₂ CH ₂ OJnH

CH.,

(m + -n = 20 P ₁ + P ₂ = 9)

(6) HO (CH ₂ CH ₂ O) In (CH ₂ CHO) P ₁ CH ₂ CHO (CH ₂ CHO) p ₂ (CH ₂ CH ₂ O) ηΗ

CH ₃
CH ₂ OCH ₃

(πι + η = 22 P ₁ + P ₂ = 20)

• * W β

/O

(71 HO (CH ₂ CH ₂ O) m (CH ₂ CHO) p ηΗ

(m + η = 24 ρ = 13)

(8) HO CCH ₂ CH ₂ O) In (CH ₂ CHO) ρ (CH ₂ CH ₂ O) ηΗ

CH ₂ OC ₃ H ₇

(m + η = 18 P = 7)

(m + n = 17 ρ = 15)

(10) · ·

(m = 21)

^C 12 ^H 25 ~ \> - ₀ (CH 0 CH ₀ 0) mC00Na (m = 51)

-Qi

O (CH ₂ CH ₂ O) InH (m = 30)

HO (CH ₂ CH ₂ O) mH (m = 68)

HO (CH _o CH _o Q) mH

According to the invention, the amount of the above-mentioned compounds

-: bond of the polyalkylene oxide type, that of the photographic Component layer must be added within in the range from 0.01 to 2.0 g per mole of silver halide, preferably from 0.03 to 1.0 g per mole of silver halide. The solvent to be used at the time of addition is water or an organic solvent mixed with Water is miscible, such as ethanol, methanol, acetone or the like.

The above solid paraffin used in photographic Component layer usable in the present invention, although it is expedient, has a particle size of not has more than 5 μm, preferably a particle size of not more than 1 μm »The particle size of the solid paraffin, which exceeds 5 μΐη, can of course also give an effect according to the invention to a certain extent, if the particle size, however becomes larger, however, with the passage of time, not only does the stability of the liquid with that dispersed therein become Paraffin or the paraffin coating liquid deteriorates, but it also becomes the transparency of the resulting coating impaired (worsened) "

The liquid or solid paraffin can according to the invention be contained in the form of a dispersed liquid in the photographic component layer. the Preparation of a dispersed liquid containing solid paraffin with the above particle size, is done by first dissolving the solid paraffin in a low-boiling solvent and then the resulting Solution, for example by means of a homogenizer in an aqueous solution of a protective colloid, dispersed such as gelatin and a surface active agent. The above-mentioned low-boiling solvent does not produce the inventive effect even if it remains in the dispersed liquid.

but it is conveniently removed either by heating or by evaporation under reduced pressure after completion of the dispersing operation.

What the addition amount of the photographic in the invention Component layer contained paraffin is concerned, it is a fact that although the effect increases with The amount added increases, but an excessively large amount of the paraffin can cause the physical properties of the component layer are impaired (worsened), so that the The amount of paraffin added is normally 5 to 100% by weight, in particular 10 to 50% by weight, based on the content of the hydrophilic binder in the paraffin-containing layer.

There are no particular restrictions on the timing of adding the above liquid or solid paraffins and the polyalkylene oxide type compound used in the present invention to the photographic component layer, however, they become useful in, for example, the formation of silver halide particles or after the end of the second ripening process is added and the photographic component layer to which they should be added is most conveniently the emulsion layer containing the silver halide, the same effect can also be achieved even if they are adjacent to it Layers or an auxiliary layer or intermediate layer on the same side of the emulsion layer on the carrier.

According to the invention, both the paraffin and the Polyalkylene oxide type compound together into the The same layer can be incorporated, but they can also be incorporated separately into different layers will. For example, the paraffin may be contained in the silver halide-containing emulsion layer

and the polyalkylene oxide type compound can be used in an adjoining (neighboring) layer or, conversely, it is also possible that the emulsion layer contains the polyalkylene oxide type compound and that the adjoining (neighboring) layer contains the paraffin.

The inventive effect based on the above-described Manner is described in more detail below:

The polyalkylene oxide type compounds having the general formula given above, especially the compounds polyoxyethylene type, have a development accelerating effect when contained in a non-lith type developer liquid, on the other hand, however, they have a development delay effect when they are in a developing liquid of the lith type are included. This particular behavior is known per se to those skilled in the art Fact. This lith development retardation effect, when the photosensitive material is processed or developed in a lith-type developer liquid, gives satisfactory photographic properties when, however, on the other hand in a developer liquid is developed of the non-lith type, an undesirable development accelerating effect is obtained as above described, whereby the fog is increased or the contrast is decreased, so that it is difficult to to achieve satisfactory photographic properties. Generally, this problem is accounted for to wear an anti-fogging agent added, but most anti-fogging agents don't just set the veil, but also the photographic sensitivity or the contrast of the light-sensitive material down and retard the lith development itself, so that the amount of the alkylene oxide type compound is decreased must, leading to impairment (deterioration) of the

photographic properties in the lith-type developer liquid.

The effect according to the invention can only occur when used of the liquid or solid paraffin in addition to those having the disadvantage described above Polyalkylene oxide type compound. This combined Use does not result in any noticeable increase in fog in non-lith type development and improves clearly the contrast in a developer liquid, regardless of whether it is of the lith type or of the non-lith type, whereby the photographic Properties are significantly improved.

The invention is described in more detail below. The composition of the silver halide used in the above, The silver halide-containing emulsion layer of the invention used must be such that it contains silver chloride in an amount of not less than 50 mol% in the whole silver halide because of the developing speed must be high if explosive development such as lith development is desired, and preferably the silver halide used should be silicon chloride bromide or silver chloride iodobromide which is not less than 60 mol% silver chloride, however contains no more than 40 mol% silver bromide and no more than 5 mol% silver iodide. These silver halides can according to the neutral process, the acid process, the ammonia process, the orderly mixing process, the reverse mixing process, the single jet process, the double jet process, the controlled double jet process, the conversion process, the core-shell process or a similar process, as in "The Theory of the Photographic Process" by James,

4th Edition, pp. 88-104, published by McMillan Publishing Co., 1977 described.

There are no particular restrictions on

the particle size, the grain size distribution, the crystal habit, the configuration (normal crystals or twin crystals and the like) and the like of the silver halide used, however, it is desirable to have a proportionate uniformly distributed particle size with silver halide with a size of not more than 1 μΐη to be used. These silver halide particles or silver halide emulsions can also be an iridium salt and / or a rhodium salt for the purpose of improving their properties compared to electronic flash light.

These silver halides can generally be obtained by the individual or combined use of sulfur sensitizers, such as sodium thiosulfate, thiourea and like; Precious metal sensitizers including gold sensitizers, such as chloro aurates, gold trichloride and the like, palladium sensitizers such as palladium chloride, Chlorpalladates and the like, platinum compounds, iridium compounds and the like; Selenium sensitizers such as selenious acid, selenourea and the like; Reduction sensitizers, such as tin (II) chloride, polyamines such as diethylenetriamine, Sulfites, silver nitrate, and the like, can be chemically sensitized, and they can also be optically sensitized are compared to any desired wavelength range through the individual or combined use of Cyanine dyes, merocyanine dyes and the like.

In the present invention, an electron trapping compound such as a metal dopant or a desensitizing dye can be used which can also be applied to a direct positive type silver halide photographic emulsion, no less contains than 50 mole percent obscured silver chloride.

Gelatin, gelatin derivatives, synthetic hydrophilic polymers or the like are used "

The silver halide emulsion layer used according to the invention can contain various photographic additives: as antifoggants, for example, azaindenes such as 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, triazoles, Thiazoles, tetrazoles, and other antifoggants known to those skilled in the art be used. Aldehyde compounds, ketone compounds, halogen-substituted acids such as mucochloric acid, Ethyleneimine compounds and the like can be used. Saponin, Lauryl or oleyl monoethers of polyethylene glycol and the like can be used. As a development accelerator For example, without the invention being limited thereto, compounds such as described can be used in Japanese OPI Patent Publication 24 427/1974, quaternary ammonium salts and the like.

Polymer latices, homopolymers or copolymers can be used as agents for improving physical properties of alkyl acrylates, alkyl methacrylates, acrylic acid and the like. Contain or consist thereof be. The silver halide emulsion layer or the other component layers of the photosensitive body of the present invention Materials may also contain an antistatic agent such as that disclosed in Japanese Patent Application No.

104 940/1977, in Japanese OPI Patent Publications 56 220/1976 and 46 733/1974 and the like. Described included.

As the support can be coated with the inventive photographic component layer, any film, such as, a polyethylene terephthalate film, a polycarbonate film, a polystyrene film, cellulose acetate film and the like. _T used.

Preferably the photosensitive is photographic Silver halide material developed by using a lith type developing liquid, though it was

. can also be developed by using a developing liquid as used for an ordinary silver halide photographic light-sensitive material. The main components of the developing liquid.; of the lith type are composed of single or mixed ^! P-dihydroxy developer compound; benzene type, such as hydroquinone, alkyl Hydro - ^"-.! quinone and halogen-substituted hydroquinone and the like.

The amount of developing agent to be added is 1 to 100 g per liter of developing liquid, preferably 10 to 30 g per liter of developer liquid.

The developing liquid may further include those given below Components and selected amounts of these components included. This component includes first a preservative for the developer compound and a sulfite (alkali metal sulfite, Alkali metal bisulfite) is used, and it is preferably used in an amount of not more than 6 g per liter Developing liquid used, although not a limitation in terms of the concentration of free sulfite ions. Sulphite ions can also be added as a buffer and aldehyde-alkali hydrogen sulfite additives, additives of soluble sulfite and a compound with a carbonyl group (^ C = O), such as additives of soluble sulphurous acid and cyclohexanone or acetone and also a mixture of the above-mentioned additives and an aliphatic primary or aliphatic secondary amine group and the like * are used as the above-mentioned buffer used and the amount of sulfite ion buffer added is to be, is 0 to 150 g per liter of developer liquid, preferably 20 to 80 g per liter Developer liquid. Further, an alkaline agent may be added to the lith type developing liquid and as the above-mentioned alkaline agent, there are used an alkali metal hydroxide, an alkali metal carbonate and an alkali metal borate and the like used and the pH of the developer liquid is pH 8 or more, in particular

which is preferably within the range of pH 9 to pH 11.

The above-mentioned lith type developer liquid can also contain other additives if required, such as pH control agents, development control agents, organic Antifoggants, antioxidants, development accelerators and organic solvents and the like.

On the other hand, the developing agent for the developing liquid used for an ordinary silver halide photographic light-sensitive material includes hydroquinone, chlorohydroquinone, dihydroquinobenzene group such as catechol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3- pyrazolidone, i-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, a 3-pyrazolidone group such as 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, N-methyl-p-aminophenol, a p-aminophenol group such as N- (4-hydroxyphenyl) glycine, β-methanesulfonamidoethyl, ethylaminotoluidine, a p-phenylenediamine group such as N, N-diethyl-p-phenylenediamine and an ascorbic acid group, and an aqueous solution containing one or contains more of the above developing agents, and besides, there can be a preservative such as potassium sulfite, a development retardant such as potassium bromide, an organic antifoggant, an alkaline agent and a buffer, an organic solvent and a development accelerator and the like are added, and the pH of the developing liquid is usually 8 to 13, preferably 9 to 12.

The invention is illustrated in more detail by the following examples, without, however, being restricted thereto.

example 1

A silver halide emulsion formed in an aqueous gelatin binder 69.8 mol% silver chloride, 30 mol%

10

Silver bromide and 0.2 mol% silver iodide was prepared by the double jet process. The prepared emulsion was chemically sensitized by noble metal sensitization using chloroauric acid in combination with sulfur sensitization using sodium thiosulfate and thereafter it was optically sensitized by adding a mero cyanine dye having the formula shown below and then added to the emulsion as well 4 -Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as a stabilizer, saponin as a coating aid and a polymer latex containing ethyl acrylate as an agent for improving physical properties, and the resulting liquid is hereinafter referred to as Liquid A without t.

20 25

Merocyanine dye

. (CH ₂ ^ 0H

On the other hand, 700 g of liquid paraffin was dissolved in 300 cm ^{3 of} ethyl acetate to make a solution. To the solution kept at a temperature of 60 ⁰ C solution was added a mixture of 200 g of gelatin, 260 cm ³ 10% Älkanol XC (a product of Nissan Fats and Oils Co., Ltd.) and 3.6 1 of pure water after the Sources added. The resulting mixture was dispersed using a laboratory-type pressure homogenizer (manufactured by Manton Gauline) under a pressure of 250 kg / cm ^{2 to} obtain a liquid with liquid paraffin dispersed therein having an average particle size of 0. 13 um received.

-vr-2o

In the same manner as above, but at a temperature of 8O ⁰ C, a liquid with dispersed therein solid paraffin having an average particle size of 0.22 was prepared μπι.

A part of the above liquid A was divided into four parts. A part thereof to which nothing was added is hereinafter referred to as Sample 1, another part to which 500 mg of Exemplified Compound (1) was added per mol of silver halide is hereinafter referred to as Sample 2, while another part, the 1, 0 g of Exemplified Compound (1) per mol of silver halide, hereinafter referred to as sample, and another portion to which 1.0 g of Exemplified Compound (1) per mol of silver halide and the above-mentioned liquid paraffin in an amount of 2.5 wt .-%, based on the hydrophilic binder, were added, is referred to as sample 4 below. Thereafter, mucochloric acid and glyoxal were added to each of the samples, and the whole were coated on a polyethylene terephthalate support so that the amount of silver was 35 mg / 100 cm ^{2 to} obtain photosensitive material samples.

Each of these samples was cut into small pieces, one of which was then exposed to tungsten light for 2 seconds through a step wedge (gray wedge). The exposed sample was subjected to a lith development at 27 ^° C. in a developer liquid A of the lith type having the composition given below.

On the other hand, another piece of each of the samples was subjected to non-lith development at 38 ^° C. in a developer liquid B having the following composition.

1 Lith-type developer liquid A

Composition a

Triethylene glycol 40 g

Polyethylene glycol

(average molecular weight 1500) 0.4 g

Formaldehyde-sodium hydrogen sulfite additives

Hydroquinone Diethanolamine Potassium Sulphite Water

Composition b

Triethylene glycol 5-nitroindazole

Ethylenediamine disodium salt tetraacetic acid boric acid
Potassium bromide Potassium carbonate Potassium sulphite Sodium hydroxide Water

25 The mixing ratio of the above compositions to water when using them was as follows:

Composition a: Composition: water = 1: 1: 4 (volume ratio)

Developer liquid B

Ethylenediamine disodium salt tetraacetic acid

5-nitroindazole

1-phenyl ~ 5-merc2ptotetrazole

Potassium hydroxide in an amount for Achieving pH

Potassium sulfite

50 , 5 G mg G 15th G G 7th G G G 1 G G ad 167 ml G 9 , 5 6th G 6th m] 2 2 50 2 1 ad 167

8th G 1 G O, 36 g 11th , 3 253 G

ir: - - _ ,. 3321630 Potassium bromide 13 g Hydroquinone 80 g Potassium carbonate 40 g Diethylene glycol 100 g 1-phenyl-4,4-dimethyl-3- pyrazolidinone 1.4 g pure water ad 1 1

When using liquid B, pure water was added to make it 4 liters.

The results obtained with these treatments or developments are given in Table I below, in which the contrast values the slope of the foot of the characteristic curves that are considered particularly important were viewed represent.

Table I.

developer A. veil contrast B. veil contrast photographic
properties 0.07
0.05
0.04
0.04 4.2
5.8
6.4
6.8 0.14
0.1 ^
0.26
0.11 3.8
3.2
2.7
3.6 Sample -1
Sample -2
Sample -3
Sample -4

As can be seen from the above Table I, it is by adding an increased amount of the compound from Polyalkylene oxide type to the paraffin-free photosensitive Material of the invention allows the photographic properties in lith-type development to improve, however, the photographic properties in the development have been of the non-lith type impaired (worse). In contrast, the combined use of both paraffin and the compound of the polyalkylene oxide type to an improvement

enhancement of the photographic properties both in the Lith-type development as well as non-lith-type development, i.e. it can be an excellent one Contrast can be achieved without increasing the haze.

Example 2

To a part of the remainder of the above-mentioned Liquid A, 700 mg of Exemplified Compound (9) was added per Moles of silver halide added to make a mixture. The mixture was then divided into 3 parts. Part of it, to which no paraffin has been added, is hereinafter referred to as sample 5, another part, to which the same amount of liquid paraffin as in the above Sample 4 was added is hereinafter referred to as Sample 6 is designated and another portion to which solid paraffin was added in the same manner is shown below referred to as sample 7. These were applied in the form of a layer and dried on the same As in Example 1 and then subjected to developments of both lith-type and non-lith-type. The results obtained are given in Table II below.

Table II

developer veil 06 A ' 4th veil 20th B ^: photographic
properties 0 04 7th 0 07 contrast Sample -5 0 04 contrast 6th 0 09 2.9 Sample ~ 6 0 6th 0 3.9 Sample ~ 7 6th 3.7 6th

20th 25th

From Table II above, it can be seen that the paraffin used in the present invention, even if it liquid or solid paraffin, led to an improvement in excellent physical properties.

Example 3

400 mg of the exemplary compound were added to the finally remaining part of the above-mentioned liquid A (4) was added per mole of silver halide, and the resulting mixture was divided into 5 parts for preparation a sample 8 containing no paraffin, a sample 9 containing the liquid paraffin in the same amount as contained in sample 4, a sample 10 which contains the liquid paraffin in twice the amount as sample 9 a sample 11 containing 50 mg of 5-nitrobenzimidazole as an antifoggant per mole of silver halide, and Sample 12 which contained 5-nitrobenzimidazole in twice the amount of Sample 11. These were in Applied in the form of a layer, dried and treated or developed in the same way as in Example 1. The results obtained are given in Table III below.

Table III

developer A. Schlei
he ■ Contrast - relative
Emofind B. Schlei
he contrast relative
Sensation photographic
properties 0.05 6.5 .lchiness
100 0.19 2.7 opportunity
176 30th Sample -8 0.04 6.7 103 0.09 3.5 179 Sample -9 0.04 6.8 101 0.06 3.7 180 Sample.-10 0.04 5.7 83 0.11 2.4 155 Sample -H 0.04 4.9 61 0.06 2.1 128 35 Sample -12

-3Λ-25

From the above Table III it can be seen that the additional use of 5-nitrobenziinidazole as Antifoggants to the samples with the combined use according to the invention have a fog-retarding effect gave, however, an adverse (inverse) effect on photographic speed or had the contrast. In contrast, the combined use of paraffin and the Polyalkylene oxide type compound according to the invention delays (limited) fogging with little or no effect on photographic Sensitivity and, in addition, an excellent contrast effect was achieved.

Claims (11)

* fl -to T 54 050 Applicant: Konishiroku Photo Industry Co., Ltd. No. 26-2 Nishishinjuku 1-chome Shinjuku-ku Tokyo / Japan PATENT CLAIMS 1 .. silver halide photographic light-sensitive material, characterized by a carrier and at least one layer applied thereon, which contains 1) silver halide grains containing at least 50 mol% Contain silver chloride, 2) liquid paraffin or finely divided solid paraffin with an average particle size of not more than 5 μm and 3) a compound that contains an alkylene oxide chain in its molecule. 2. Material according to claim 1, characterized in that the compound has one of the following formulas: I ₁ O (CH ₂ CH ₂ O) In ₁ (CH ₂ CHO) ρ _χ (R ₃ O) U ₁ (CH ₂ CHO) ρ ₂ (CH. R ₁ ( ₂₂ ) _{1 2} ρ _{χ 2 1 2 2 22 23} CH ₂ R ₄ CH ₂ R ₄ or R ₇ O (R ₃ O) n ₃ (CH ₂ CH ₂ O) In ₅ R ₈ (III) where mean: R., R_, R _1. , R _fi , R ₇ and R _ft hydrogen, an alkyl, aryl or acyl radical, R ₀ -CHoCH- or -CH ₀ CH ₀ CH ₉ CH ₉ -; ² ^ 2 2 2 2 ₀
² R and Rg are hydrogen, an alkyl or cycloalkyl radical with 1 to 4 carbon atoms or an alkoxy radical with 1 to 8 carbon atoms, n ₁ , n ₂ and n ₃ an integer from 0 to 5, P ₁ + P ₀ F Po ⁺ P ₄ an integer from 0 to 60 and m ^ m F ^m 3 ^{+ m} 4 ^{un (} ä πι, - a integer from 10 to 80. 3. Material according to claim 1 or 2, characterized in that it is the compound in an amount of 0.01 to Contains 2.0 g per mole of silver halide. 4. Material according to one of claims 1 to 3, characterized characterized that it is the paraffin in an amount of Contains 5 to 100% by weight compared to a hydrophilic binder.
20th 5. Material according to any one of claims 1 to 4, characterized in that the silver halide grains have an average size of 0.1 to 1 µm . 6. Material according to any one of claims 1 to 5, characterized in that the paraffin and the compound in different layers are included. 7. Material according to one of claims 1 to 5, characterized characterized in that the paraffin and the compound are contained in the same layer. 8. Material according to any one of claims 1 to 7, characterized in that the silver halide grains from Silver chloride, silver bromide and carbon iodide exist. 9. Material according to any one of claims 1 to 7, characterized in that the silver halide grains from Silver chloride and silver bromide exist. 10. Material according to one of claims 1 to 9, characterized characterized in that the paraffin has an average 5 Particle size of 0.05 to 5 μΐη has. 11. Material according to one of claims 2 to 10, characterized in that ρ -, + ρ ^ »Po ⁺ P ^ is an integer of 0 to 30 mean. 10