DE3151190A1 - METHOD FOR DEVELOPING LIGHT-SENSITIVE PHOTOGRAPHIC SILVER HALOGENIDE MATERIALS - Google Patents

Description

The present invention relates to silver halide photographic light-sensitive materials (hereinafter referred to as for convenience referred to as "silver halide photosensitive materials") and in particular silver halide light-sensitive materials that have been acid processed or acid processed Having gelatin in a surface layer thereof.

Silver halide photosensitive materials generally contain a support such as a plastic ilm or a plastic film, paper or a polymer-coated paper, at least one Silver halide emulsion layer and as the case may be special material other types of layers, such as one Interlayer, a surface protective layer, a filter layer, an antihalation layer, a Backing layer, etc., on the support.

Binders used to form the "layers" on the 3Q support usually contain hydrophilic colloids such as gelatin. Gelatin is usually used as a binder, even for the preparation of surface layers, such as a surface protective layer and a backing layer. The use of gelatin in the surface layer

but leads to an increase in the adhesiveness or tackiness of the surface at high humidity, especially in an atmosphere of high temperature and high humidity. When the surface layer comes into contact with other materials under such conditions, it sticks easy on it.

The adhesion phenomenon can be between photographic materials themselves or between photographic Materials and other materials that occur with it during production, photography, the processing, projection or storage of the photographic materials come into contact with what often leads to problems.

In order to solve the adhesion problem, which is well known, a method is used in which fine particles of inorganic substances such as silicon dioxide, silver halide and titanium dioxide and organic substances such as polymethyl methacrylate having a grain size of about 0.3 μm to 5 μm are used ψ, to be incorporated into a surface layer to reinforce the roughness of the surface, ie

to cause a matting and thus the stickiness to reduce the surface layer. However, the addition of a large amount of the matting agent results to various disadvantages. For example, the matting agent aggregates in a coating solution, whereby

® it becomes impossible to obtain a uniform coating layer to build. The sliding properties are deteriorated, resulting in easy photographic scratching Materials leads; the leadership: i properties of films in a photography or projection

Devices are deteriorated; the transparency

the number of images formed is reduced; the graininess of the images increases, thereby deteriorating the image will.

In order to overcome the above problems, JA-OS No. 104926/75 describes a method of incorporation of acid processed gelatin and silica anhydride colloid in a surface layer, the JA-OS No. 13 7129/75 describes a method under Using acid processed gelatin in combination with alkali processed gelatin in a surface layer, the JA-OS No. 160034/75 describes a method for incorporating with Acid processed gelatin and an organic fluorine surfactant into one surface layer, and JA-OS No. 6017/76 describes a method using acid processed Gelatin and a matting agent in

a surface layer. 20th

The high-temperature rapid processing in the manufacture or development of photosensitive Silver halide materials give the so-called

"Reticulation" - phenomenon that; appear in shifts C

may contain gelatin as a binder. To prevent such reticulation or crosslinking, the JA patent publication describes No. 43777/76 a technique for incorporating acid processed gelatin with gel strength

("Jelly strength") of 250 g or more (determined with a gel strength or jelly strength measuring device of the Bloom type according to the PAGI method, described in Shashinyo Gelatin Shikenho, published by

Shashinyo Gelatin Shikenho Godo Shingikai, p. 5 35

(197O)) into the surface layer.

As described above, various tests / physical properties were made of light-sensitive silver halide materials using acid-processed gelatin

5 tine to improve.

However, it has been found that although through the use in front of acid processed gelatin in a surface layer the physical properties can be improved, but there is a disadvantage that impurities such as oxidized products at the stage of development processing of developing agent easily on the surface of such silver halide light-sensitive materials be liable. These impurities, which are adhered in the stage of development processing, greatly deteriorate the image quality after development processing. In particular adhere to the processing of a light-sensitive silver

² ^ halide material with an automatic developing device, the oxidized products of the developing agent, which are present on a conveying roller of the automatic developing device, easily adhere to the surface of the silver halide light-sensitive material, thereby deteriorating the image quality considerably.

The main aim of the invention is to provide photosensitive silver halide materials

materials with excellent physical properties, such as resistance to adhesion and reticulation or crosslinking and where in addition, no contamination during the

Adhering development processing. 35

It has now been found that this aim of the invention

/ 70

can be achieved by developing photosensitive Silver halide material with a surface layer that has been processed or treated with acid. having acid processed gelatin as a binder, in the presence of compounds that act through Formula I shown below can be represented.

The invention therefore relates to a method for developing a photosensitive. Silver halide material, the one support and at least one light-sensitive silver halide emulsion layer on the support, wherein a surface layer of the light-sensitive material with acid or acid-processed gelatin as a binder, the development being carried out in Presence of a connection, represented ·: by the Formula I.

•Re

R ₁
CH-

\
η

- R

CH
I '

Ra

^R 5

CH

CD

wherein R is a saturated or unsaturated aliphatic group of 7 to 22 (and preferably 8 to 15) Is carbon atoms or a substituted aryl group,

is a hydrogen atom or a methyl group;

»■ - 3151

R- and R ^ each represent an alkyl group or substituted oine An alkyl group (e.g., an alkoxyalkyl group and a hydroxyalkyl group) having 1 to 4 carbon atoms are;

R- and Rj. Each represent a hydrogen atom or a Are alkyl groups with 1 to 4 carbon atoms,

L has the meaning of -CONH-, -SO ₂ NH-, -0-, -S-, -CONH (CH ₂ J) ₁ -O-, -SO ₂ NH (CH ₂ J ₁ -O; 0

ti

-P-NH- or -0-CH ₀ CH-;

I ^ l

OH OH

m is 0 or 1, η is 0, 1, 2 or 3, χ is 0, 1, 2 or 3, A is -C00 ^@ or -SO ₃ ⁰ ; and

1 is an integer of 2 or more (preferably 2 to 5).
20th

Preferred examples of the substituted aryl group R in Formula I are represented by the formula Ia

(la)

wherein R 'is a saturated or unsaturated aliphatic Is a group of 7 to 21 carbon atoms, y is 0 or 1 and n is 1 or 2.

Typical examples of compounds represented by Formula I are listed below:

Connection 1.

-χ-1 ζ

²⁵ connection 4

CH ₃

^H ₂ f [- ^CH 2 ^{C0 (P} CH,

Connection 2

CH,

Connection 3

CH,

I & - CH ₉ COC

CH,

CH, C ₁₃ H ₂₇ CONHCH ₂ CH ₂ CH ₂ OCH ₂ CHfN -

CH,

Connection 5

^C 8 ^H 17

CH-CH-OH

ι Δ L

OCH ₂ CH ₂ CH | N - CH ₂ CH ₂ CH ₇ CH ₂ SOY j

CH ₂ CH ₂ OH

-Jf-0

link

^C 15 ^H 31

CH,

CH,

Connection CH,

SO ₂ NHCH ₂ CH ₂ CH®N -

CH,

Compound CH ₃

© I 0 C _1C .H ₇₇ CONHCH ₂ CH ₂ CH ₂ N - CH ₂ COO

'IS-

Connection CH,

CH ₀ CH ₉ OCH

CH,

Compound ^ - CH ₂ CH ₂ COO CH ₃

link

^C 11 ^H 23 ⁽

CH.

CH

Connection 12-

C ,, H ₉₇ OCH ₉ CH -

CH,

CfJf-N - CH ₉ C00 ^Q

Z ι t>

OH CH,

link 1 1 3 - CH
I. ₂ CH ₂ OH : h ₉ chq Δ ι. - CH ₂ CH ₂ OH ^C 14 H 29 ^OC I.
OH CH ₂ coo ^Q _t link 4th

CH ^

tra - CH ₇ COcK

■ CH, -

Link

CH.

C ₈ H ₁₇ SO ₂ NHCH ₂ CH ₂ CH ₂ OCH ₂ CiO

CH

1 Preparation example 1

Synthesis of compound 1
1. Production of N-dodecyl-N / N-dimethylamine

A 2-1 three-necked flask fitted with a Thermometer, a stirrer and a dropping funnel, 185 g (1 mol) of dodecylamine and 300 ml of ethanol are charged. After dissolving the dodecylamine in the ethanol, 260 ml of 85% Formic acid was gradually added dropwise through the addition funnel while maintaining the temperature

was kept at 30 ° C with stirring. After this

completed dropping, 210 ml 37 wt .-%

Formaldehyde added dropwise in the same way. The resulting mixture was 1 h at 40 ° C stirred. Then the flask was in

a hot water bath is used, and the mixture 20

was refluxed for about 3 h until none

Carbon dioxide gas was more developed.

After reflux, the reaction solution was cooled and a 30% aqueous solution of sodium-25

hydroxide was gradually added to the solution until basic dissolution. Afterward 400 ml of benzene was added to the solution, and the resulting mixture was carefully in

_o . shaken in a separating funnel and then left to stand, whereupon it separated into two layers. The top layer, ie the benzene layer, was removed from the flask and dried over potassium carbonate overnight.

■ _c closing the benzene was distilled off and the residue was decentralized under reduced pressure

-Κ

ι stylized, with the formation of 170 g of N-dodecyl-N, N-dimethylamine (bp 94 ° C / 1.33 inbar or 1 romHg; Auabeubfi ΠΟ %).

5 2. Establishing the connection 1

A 500 ml three-necked flask equipped with a thermometer, a stirrer and a condenser was charged with 106.5 g (0.5 mol) of N-dodecyl-N ^ N-dimethylamine. An aqueous solution of sodium monochloroacetate, which had been prepared according to the method explained below, was added, and the mixture was stirred on an oil bath ^{at a temperature of 95 to 100 ° C. for 4 hours.}

With the course of the reaction, the reaction solution became gel-like and could not be stirred. A small amount of ethanol was therefore added at this point.

The reaction solution was poured into a 1-1 flask from Egg type was introduced, and the water and ethanol were distilled off under reduced pressure. The residue was added to and dissolved in 400 ml of ethanol, and the insoluble by-product Sodium chloride (NaCl) in the ethanol was filtered off. After distilling off the Ethanol, 300 ml of acetone was added to the resulting residue. The mixture was in the flask equipped with a condenser

to dissolve the residue in acetone and the solution was filtered. After cooling the filtrate crystals precipitated out with ice.

These crystals were filtered off and dried in a desiccator to give 57.1 g

-ο Ί b I

* of compound 1. The yield was 42%; the melting point could because of the high moisture absorption of connection 1 cannot be measured.

3. Production of sodium monochloroacetate

A solution of 22 g (0.55 mol) of sodium hydroxide in 25 ml of water became a solution of 51.7 g (0.55 mol) monochloroacetic acid added in 60 ml of water with suitable cooling so that the temperature Did not exceed 50 ° C. The reaction solution was adjusted to pH 6.0 to 7.0

set. 15th

Production example 2

Synthesis of compound 2

1. Preparation of 3-myristylamidopropyl-N, N-dimethylamine

A 2-1 three-necked flask equipped with one

Cooling tube was filled with 122.5 g (1.2 mol) of N, N-dimethylaminopropylamine and 12 charged 3.4 g of acetonitrile. The mixture was cooled with ice with stirring 3Q and at a temperature of 10 C or held less.

Then 246.8 g (1 mol) of myristyl chloride, which had been prepared in the usual manner, dropwise to the mixture during 1 h was added and the temperature was increased to 60.degree

raised. The mixture was stirred at this temperature for 1 hour and then poured into 2 liters of powdered ice. The precipitated crystals were filtered off and air-dried overnight. The crystals were recrystallized from acetone to obtain 235 g of S-Myristylamidopropyl-NJN-dimethylamine (mp. 45 to 5O ⁰ C, yield 75%).

10 2. Establishing the connection 2

A mixture of 106 g (0.5 mol) of 3-Myristylamidopropyl-N, N-dimethylamine, 47.2 g (10.5 mol) of chloroacetic acid and 15Og of methanol were charged into a ¹ ^ 1-1- three-necked flask equipped with a cooling tube , and kept at a temperature of 10 C or less by cooling with ice while stirring.

Then 97 g (0.5 mol) of a 28% methanol solution of sodium methoxide was added to the above The solution prepared was heated dropwise to 60 ° C. for 30 min, and it was at this Stirred temperature for 4 h. The reaction solution was allowed to cool at room temperature, and it a partially soluble product then precipitated out and was removed by filtration. Afterward 1.2 L of acetone was added to the insoluble products separated above. The precipitated

Crystals were filtered off, dried and

dissolved in 300 ml of isopropanol by heating. The insoluble portion was separated by filtration with heating and added to 1 liter of acetone.

After cooling with ice, the precipitated 35

Crystals filtered off and stored at a temperature

dried from 50 to 60 ° C. to give 124 g of compound 2 (yield 67%).

Production example 3

Synthesis of compound 3

1. Preparation of 3-laurylamidopropyl-N, N-dimethyl ~ amine

A mixture of 200 g (1 mol) of lauric acid and 122.4 g (1.2 mol) of N, N-dimethylaminopropylamine (boiling point 140 ° C.) was placed in a 500 ml flask and cooled in a nitrogen (N ₂ ) Gas stream kept under reflux at a temperature of 100 ° C. for 6 h.

At this temperature, a major part of the reaction by-product became water and excess Amine removed from the reaction system and then they became under reduced pressure

completely distilled off. 25th

Then, 600 ml of ethyl acetate was added to the resultant Added residue, which was dissolved therein by heating. When cooling the solution with ice

white crystals precipitated. These white crystals 30

were filtered off and dried

The solution was further concentrated, and with ice Once cooled, crystals separated out again.

These crystals were separated by filtration, 35

united with the first deposited crystals,

2 ₀ - '■' ■ '■ ' - '-3 1 5 1Ί

mixed well and then dried in a desiccator. 200 g (yield 65%) of the desired product (melting point 39 to 40 ° C.; yield 56 to 65%) were obtained in this way .

5.

2. Establishing the connection 3

A 1-1 eggplant-type flask was fitted with 190 grams (0.67 moles) of 3-laurylamidopropyl-N / N-dimethylamine loaded. An aqueous solution of sodium monochloroacetate prepared according to the one described below Method had been prepared, and 400 ml of ethyl acetate was added and the resulting Mixture was 5 to 6 h on one

15 oil bath kept under reflux at 120 ° C.

After the reflux, the pH of the reaction solution was adjusted by adding dropwise hydrogen chloride acid adjusted to 5.5 to 6.0. After adjusting the pH, the water and the Ethanol distilled off under reduced pressure, and the residue was dried.

Then 1.5 1 of ethanol were added to the residue _r which was then dissolved therein by heating. Insoluble sodium chloride and excess sodium acetate were separated by filtration and the ethanol was distilled off. Then about 1.5 l of petroleum ether were added to the residue

and the resulting mixture was stirred

and then left to stand overnight.

The petroleum ether was decanted off and successively the solvents were completely reduced Distilled pressure. The residue was ■

dried to give compound 3 as a pale yellowish solid (yield 90%).

3. Preparation of aqueous sodium monochloroacetate solution

A solution of 32 g (0.8 mol) of sodium hydroxide in 30 ml of water became a solution of 75.6 g (0.8 mol) Monochloressxgsaure added in 70 ml of water with suitable cooling, so that the temperature Did not exceed 50 ° C. The pH of the sodium monochloroacetate solution was increased by adding from sodium hydroxide (NaOH) to 9.0 to 10.0

* ° posed.

example

2Q -

Synthesis of the compound 13

1. Production of a co-tetradecyl cc -'-cblorhydrin ether

A 2-1 three-necked flask fitted with a Stirrer, a reflux condenser and a thermometer, 1.284 g (6 mol) of tetradecyl

QQ alcohol loaded. Then 2.0 to 2.6 g (0.008 to 0.01 mol) of tin tetrachloride was added as a catalyst. The mixture was carefully stirred and 148 g (1.6 mol) of epichlorohydrin were added all at once. The mixture was

heated and 30 min at 100 ⁰ C and 2 to 3h at

IZ

Stirred from 120 to 130 ° C. After cooling the reaction solution a small amount of aqueous potassium carbonate solution was added to 45 to 50 ° C. The mixture was then vigorously stirred to decompose the catalyst. It then became anhydrous Sodium sulfate was added to the dry solution, and then the solution was separated by filtration. The filtrate thus obtained became subjected to vacuum distillation, with formation of the desired product (b.p. 176-18O ° C / '. 3.99 mbar or 3mmHg; Yield 345g, 70% des theoretical value based on the amount of epichlorohydrin).

¹⁵ 2. Production of tetraglycidyl ethers

A 1-1 three-necked flask fitted with a A reflux condenser, a stirrer, a thermometer and a dropping funnel were added with 343 g (1.12

² ^ moles) of a chlorohydride diet. While heating at a temperature of 85 to 90 ° C, a 25 to 30% aqueous solution of caustic soda (containing 60 g or 1.5 moles of caustic soda) was added dropwise with vigorous stirring, and then the mixture was vigorously at a temperature stirred from 95 to 100 C for 5 h

After confirmation by the Beilstein flame

reaction that the solution contained no chlorine, the solution was cooled to room temperature and ditched. The solution separated into two layers. The top layer was separated, diluted with a suitable amount of ether,

dried over anhydrous potassium carbonate and

distilled in vacuo to achieve the desired Product (bp 156-16O ° C / 3.99 mbar resp. 3 mmHg; Yield 290 g; 95% of the theoretical value).

3. Production of N * - (2-Hydroxy-3-tetradecyloxypropyl) N, N-dihydroxyethyl

A mixture of 289 g (1.07 mol) of glycidyl ether and 113 g (1.07 mol) of diethanolamine was placed in a 1-1 eggplant type flask, and 300 ml of isopropanol was added. The mixture was refluxed for 3 hours and the isopropanol was then distilled off.
15th

4. Establishing the connection 13

4.1 Production of sodium monochloroacetate

A solution of 48 g (1.2 moles) of caustic soda in 60 ml of water gradually became a solution of 113 g (1.2 mol) of monochloroacetate in 80 ml of water with cooling at a temperature of 50 ° C or less to produce a

aqueous solution of sodium monochloroacetate. 25th

4.2 Establishing the connection 13

A mixture of 410 g (1.09 mol) of N- (2-hydroxy-3-tetradecyloxypropyl) -N, N-dihydroxyethyl and 113 g (1/2 mol) of monochloroacetate in 80 ml of water was placed in a 1-1 three-necked flask _f fitted with a stirrer and a thermometer, and. then 50 ml of dioxane were added. The mixture was stirred at a temperature of 95 to 100 ^° C. for 5 h. Subsequently was

the mixture cooled, washed with petroleum ether and concentrated to dryness. The so obtained Solids were dissolved in 2 to 2.5 liters of methanol with heating, and the insoluble sodium chloride and excess sodium monochloroacetate were removed by filtration. The methanol was from distilled off from the filtrate, and the resulting residue was dried to obtain 450 g of compound 13 (95% of theoretical).

The compound represented by the formula I, as used in the present invention is added to a hydrophilic colloid layer or multiple layers (for example, a silver halide emulsion of a surface protective layer is _t an intermediate ^ layer and a backing layer) or to a development processing solution together. In particular, it is preferred to incorporate the compound in the surface protective layer of the silver halide light-sensitive material.

If the compound represented by the formula I is incorporated into the hydrophilic colloid layer, so is the amount added in general

- 6-3

1.0 x 10 to 1.0 x 10 moles and preferably

- 5–4

1.0 x 10 to 1.0 χ 10 mol per g of binder

the hydrophilic colloid layer.

On the other hand, it becomes the compound in the development processing solution introduced, the amount of compounds added is generally 0.1 to 10 g, and preferably 0.5 to 3 g per liter of the development processing solution.

-ΛΟ-

The acid-processed gelatin used here is made by applying a treatment using, for example, hydrochloric acid in the process of making them from collages,

^ With porcine skin, bovine bone or the like. As the starting material and differs from alkali-processed gelatin which is produced by applying a treatment using for example lime, which is typically used in the graphic arts industry photo- ^ ^1.

Methods for making acid-processed gelatin and alkali-processed gelatin and their properties are described in more detail in Arther Veis, The Macromolecular Chemistry of Gelatin, Academic Press, pp. 187-217 (1964). The main difference between the acid-processed gelatin and the alkali-processed gelatin is that the isoelectric point of the acid-processed

ten gelatine is between pH 6.0 and pH 9.5, whereas that of the alkali-processed gelatine lies between pH 4.5 and pH 5.3.

Preferably, the one used according to the invention has

Acid-processed gelatin has a gel strength or jelly strength (determined by the i'AGI method using a Bloom type gel strength meter) of 200 g or more, and preferably

from 240 to 300 g. 30th

Examples of the surface layers on the invention silver halide photosensitive material used include a surface protective layer and a back layer. In addition to the Acid-processed gelatin can, if desired,

'*''' ■ - "' -'- 3151Ί

other hydrophilic colloids such as alkali-processed gelatin, modified gelatin, polyvinyl alcohol and polystyrene sulfonic acid can be incorporated into the surface layer as a binder.

However, it is preferred that the acid-processed gelatin contain at least 80% by weight of the binder, contained in the surface layer represents.

Examples of the photosensitive ones used in the present invention Silver halide materials include a color negative film, a color positive film Color paper, a color reversal film, a black and white negative film, a X-ray film, a printing film and a microfilm.

The following are the construction, exposure and development processing of the present invention described silver halide photosensitive material.

The light-sensitive silver halides that may be used in the present invention comprise silver halide photosensitive materials, SiI-berbromid, Silbarjodbromid, silver iodochlorobromide, silver chlorobromide and silver chloride _t

The grain size distribution can be narrow or broad. 30th

The silver halide particles in the photographic emulsion can be in any regular crystal form, e.g. in cubic and octahedral forms, in irregular crystal form, e.g. spherical and planar Forms, and in a compound crime

stable form are available from it. The silver halide can also be a mixture of particles with different crystal shapes be.

The silver halide particle may consist of an internal phase and a surface phase separate from each other are different, or can consist of a uniform phase. It can also be a Particles in which a latent image is mainly formed on its surface, or it may be a particle in which the latent image is formed in its interior.

In the course of the formation of silver halide particles or their physical ripening, cadmium salts, Zinc salts, lead salts, thallium salts, iridium salts or its complex salts, rhodium salts or its complex salts, iron salts or its complex salts and the like. Be present in combination to the sensitivity, the stability over time, and the sensitivity to high intensity exposure to improve. In the silver halide emulsion used in the present invention, various Compounds are incorporated to during manufacture, storage, or photographic processing of the photosensitive material or the photographic performance to stabilize.

Compounds that can be used for this purpose include azoles, e.g., benzothiazolium salts, Nitroindazoles, triazoles, benzotriazoles and benzimidazoles (especially nitro and halogen substituted compound); heterocyclic mercapto compounds, e.g. mercaptothiazoles, mercaptobenzothiazoles,

Mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially i-phenyl-S-mercaptotetrazole), and mercaptopyrimidines; heterocyclic mercapto compounds containing water-soluble groups, such as a carboxyl group and a sulfone group .; Thioketo compounds, e.g., oxazolinethione; Azaindenes, e.g., tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) -tetraazaindenes); Benzenethiosulfonic acids and benzenesulfinic acids. These compounds are known as antifoggants or stabilizers.

The details of such connections and a method their use is described, for example, in U.S. Patents 3,954,474, 3,982,947 and 4,021 and JA Patent Publication No. 28660/77.

Silver halide emulsions are generally chemically sensitized. For chemical sensitization the method as described in H. Frieser ed., The Basics can be used of the photographic processes with silver halides, Akademische Verlagsgesellschaft, S-. 675 to 734 (1968). For example, a sulfur sensitization method using sulfur-containing compounds suitable for the reaction can be performed with active gelatine and silver (e.g. thiosulfates, thioureas, mercapto compounds and Rhodanine), a reduction sensitization method

^ou using reducible substances (e.g.

Tin IV salts, amines, hydrazine derivatives, formamizinsulf insic acid and silane compounds); and a noble metal sensitization method using noble metal compounds (e.g. gold complex salts and Complex salts of metals of group VIII of the period

-31 51

systems (such as Pt, Ir and Pd) can be used alone or in combination with each other.

The sulfur sensitization method becomes more accurate described, for example, in U.S. Patents 1,574,944, 2,410,689, 2,278,947, 2,728,668, and 3,656,955, which Reduction sensitization method, for example, in U.S. Patents 2,983,609, 2,419,974 and 4,054,458 and the noble metal sensitization method in, for example, U.S. Patents 2,399,083, 2,448,060 and US Pat GB-PS 618 061.

The hydrophilic colloid layer of the silver halide light-sensitive material of the present invention can contain inorganic or organic hardeners. Examples of such hardeners are chromium salts (e.g. Chrome alum and chrome acetate), aldehydes (e.g. formaldehyde, glyoxal and glutaraldehyde), N-methylol compounds (e.g. dimethylolurea and methylol dimethylhydantoin), dioxane derivatives (e.g. 2,3-dihydroxydioxane), active vinyl compounds (e.g. 1,3,5-triacryloyl-hexahydro-s-triazine and 1,3-vinyl-sulfonyl-2-propanol), active halogenated compounds (e.g. 2,4-dichloro-6-hydroxy-s-triazine) and mucohalogenic acids (e.g. mucochloric acid and mucophenoxychloric acid). These compounds can be used alone or in combination with each other.

The photographic emulsion according to the invention

SO

is used, it can be subjected to spectral sensitization with methine dyes, etc. These sensitizing dyes can be used alone or can be used in combination with each other. Combinations of sensitizing dyes

35 '

often used, especially for the super color

awareness raising. In combination with such sensitizing dyes dyes that do not themselves have any spectral sensitizing effect, or substances that do not substantially absorb visible light but have super color sensitization exercise can be incorporated into the photographic emulsion.

Suitable sensitizing dyes, combinations of dyes giving super color sensitization and substances giving super color sensitization in Research Disclosure, Vol. 176, Item 17643, p. 23, IV-J, December

Described in 1978. 15th

The photographic emulsion layer or other hydrophilic colloid layers of the light-sensitive silver halide material according to the invention may contain various surface active agents, ^ ® for various purposes, for example, to facilitate coating formation, to prevent the generation of static electricity, to improve the sliding properties, to emulsify and to disperse Prevention of adhesion and improvement of photographic characteristics (e.g. acceleration of development, enhancement of contrast and sensitization).

Surfactants used for such purposes

Can be used include nonionic surfactants, such as saponin (steroid based) Alkylene oxide derivatives (e.g. polyethylene glycol, condensates of polyethylene glycol and polypropylene glycol,

Polyethylene glycol alkyl ether or polyethylene glycol 35

alkylaryl ethers, polyethylene glycol esters, polyethylene

glycol sorbitan esters, polyalkylene glycol alkylamines or alkylamides and polyethylene oxide adducts of

or silicon
Silicone? Glycidol derivatives (e.g. alkenyl amber

acid polyglyceride and alkylphenol polyglyceride), 5

aliphatic ^ esters of polyhydric alcohols and alkyl esters of sugars; anionic surfactants Agents / containing acidic groups, such as a carboxy group, a sulfo group, a phospho group, a Sulphate group and a phosphate group, e.g. alkyl carboxylic acid salts, Alkyl sulfonic acid salts, alkylbenzenesulfonic acid salts, alkylnaphthalene sulfonic acid salts, Alkyl sulfates, alkyl phosphates, N-acyl-N-alkyltaurines, Sulfosuccinates, sulfoalkyl polyoxyethylene-alkylphenyl ethers and polyoxyethylene alkyl phosphates; amphoteric surfactants, such as amino acids, aminoalkylsulfonic acids, Aminoalkyl sulfates or phosphates, alkyl betaines and amine oxides; and cationic surfactants Agents such as alkylamine salts, aliphatic

cal or aromatic quaternary ammonium salts, 20

heterocyclic quaternary ammonium salts, e.g.

Pyridinium and imidazolium compounds and aliphatic or heterocyclic ring-containing phosphonium or sulfonium salts. In addition, fluorinated te surfactants can be used. 25th

Suitable examples of such surface-active agents Agents are described in U.S. Patents 2,240,472,

2 831 766, 3 158 484, 3 294 54O _r 3 507 b60, 2 739 891, _o _ 2 823 123, 3 415 649, 3 666 478, 3 756 828, 3 133 816,

3 441 413, 3 545 974, 3 726 683, 3 843 368, 2 271 623, 2 944 900, 3 253 919, 3 589 906, GB-l'Sen 1 012 495, 1 022 878, 1 179 "290, 1 198 450, 1 397 218, 1 138 514, 1 159 825, 1 507 961, 1 503 218, BE-PS 731 126, DE-OS 19 61 638, JA-OSen 117414/75, 59025/75 , 21922/78 etc.

Of these surfactants, particularly preferred are anionic surfactants with a suIfogroup.

The photographic emulsion layer of the silver halide light-sensitive material of the present invention may contain color-forming couplers, i.e. compounds suitable for color formation by oxidative coupling with aromatic primary amine developers (e.g. phenylenediamine derivatives and aminophenol derivatives) in color development processing. Couplers that can be used include Magenta couplers such as a 5-pyrazolone coupler, a pyrazolone imidazole coupler, a Cyanoacetyl coumarone couplers and a closed acylacetonitrile coupler, yellow couplers such as acylacetamido couplers (e.g. benzoylacetoanilide and ewaloylacetoanilide) and cyan couplers such as a naphthol coupler and a pheno! coupler. Of these couplers, non-diffusion type couplers are those of a hydrophobic type Have a group (a so-called ballast group) in the molecule, preferred. Any 4-equivalent and 2-equivalent couplers can be used. Colored couplers with the color correction effect or coupler that one ° Release development inhibitors during development (so-called DIR couplers) can be used. Additionally such DIR couplers can be non-color-forming DIR coupler compounds that produce a colorless product through coupling reaction and release of a

development inhibitor can be used.

Suitable examples of magenta couplers are described in U.S. Patents 2 788 6OO, 2983608, 3062653, 3127269, 3311476, 3419391, 3519429, 3558 3-19, 3,582,322, 3 615 506, 3 834 908, 3 891 445, DE-PS

^: "'" · "·'"' · ^: 31 51 -2 * · -

18 10 464, DE-OSes 24 08 665, 24 17 945, 24 18 and 24 25 467, the JA patent publication 6031/65 JA ~ 0Sen 20826/76, 58922/77, 129538/74, 74027/74, 159336/75, 42121/77, 74028/74, 60233/75, 26541/76 and

5 55122/78 etc.

Suitable examples of yellow couplers are described in U.S. Patents 2,875,057, 3,265,506, 3,408,194, 3,551,155, 3,582,322, 3,725,072, 3,891,445, the DE-PS 15 47 868 in DE-OSes 22 19 917, 22 61 361, 24 1.4 006, GB-PS 1 425 020, JA patent publication 10783/76, JA-OSes 26132/72, 73147/73, 102636/76, 6431/75 , 123342/75, 130442/75, 21827/76,

87650/75, 82424/77, 115219/77 etc. 15

Suitable examples of cyan couplers are described in U.S. Patents 2,369,929, 2,434,272, 2,474,293,

2 521 908, 2 895 826, 3 034 892, 3 311 476, 3 458 315,

3 476 563, 3 583 971, 3 591 383, 3 767 411, 4 004 929,. DE-OSes 2 414 830, 2 454 329, JA-OSes 59838/73, 26034/76, 5055/73, 146828/76, 69624/77, 90932/77, etc.

Suitable couplers that can be used are described in U.S. Patents 3,476,560, 2,521,908, 3,034,892, JA patent publications 2016/69, 22335/63, 11304/77, 32461/69, the JA-OSen 26034/76, 42121/77 and the DE-OS 2 418 959.

DIR couplers that can be used are 30

described in U.S. Patents 3,227,554, 3,617,291, 3,701,783, 3,790,384, 3,632,345, DE-OSes 24 14 006, 24 54 301, 24 54 329, GB-PS 953 454, the JA-OSen 69624/77, 122335/74 and the JA patent publication

16141/76. 35

In addition to DIR couplers, the light-sensitive Material contain other compounds that inhibit development in development release as mentioned above. For example, the compounds described can be used are in the üS-PSs 3 297 445, 3 379 529, the DE-PS 2 417 914, the JA-OSes 15271/77 and 9116/78.

These couplers can be incorporated into the silver halide emulsion layer incorporated by conventional techniques, such as that described in US Pat. No. 2,322 described method. For example, the coupler is used in alkyl phthalate (e.g. dibutyl phthalate and Dioctyl phthalate), phosphoric acid esters (e.g. diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and Dioctyl butyl phosphate), citric acid esters (e.g. tributyl acetyl citrate), benzoic acid esters (e.g. octyl benzoate), Alkylamides (e.g. diethyl laurylamide), aliphatic acid esters (e.g. dibutoxyethyl succinate and dioctyl azelate), trimesic acid esters (e.g. Tributyl trimesiate) or the like. Or in organic Solvents with a boiling point of about 30 to 150 C, such as lower alkyl acetates, e.g. ethyl acetate and butyl acetate, ethyl propionate, sec-butyl alcohol, Methyl isobutyl ketone, ß-Äthoxyäthylacetat and Methylcellosolve acetate dissolved and then in one hydrophilic colloid dispersed. The above-described organic solvents with high Boiling point and the organic solvents with

^u low boiling points can also be used in a mixture with one another.

There can also be used a method of dispersion using the polymeric substances, which are described in the JA patent publi-

1 solution 39853/76 and the JA-OS 59943/76.

In the case of couplers with an acidic group, ζ. B-one Carboxylic acid and a sulfonic acid will turn these into the hydrophilic colloid in the form of an alkaline aqueous solution incorporated.

If necessary, matting agents such as silicon dioxide and polymethyl methacrylate can be used in finer form Particles (with a grain size of 1 to 10 pn or u) and lubricants such as colloidal silicon dioxide in the surface layer of the silver halide light-sensitive material of the present invention is incorporated will.

In the practice of the invention, known anti-fading agents such as hydroquinone derivatives, Gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives and bisphenols can be used in combination. Color image stabilizers like the one here can be used alone or as a mixture containing two or more thereof.

Suitable examples of hydroquinone derivatives are described in US Pat. Nos. 2,360,290, 2,418,613, 2 675 314, 2 701 197, 2 704 713, 2 728 659, 2 732 300, 2 735 765, 2 710 801, 2 816 028, in GB-PS 1 363 921 etc.

Suitable examples of gallic acid derivatives are described in US Pat. Nos. 3 457 079, 3 069 262 etc.

Suitable examples of p-alkoxyphenols are described in ÜS-PSs 2,735,765, 3,698,909, in JA-patent publications 20977/74 and 6623/77 etc.

Suitable examples of p-oxyphenol derivatives are described in U.S. Patents 3,432,300, 3,573,050, 3,574,627, 3,764,337, in JA-OSes 35633/77, 1474 * 34/77 and 152225/77 etc.

Suitable examples of bisphenols are described in U.S. Patent 3,700,455.

The silver halide light-sensitive material according to the invention can contain ultraviolet absorbers contain hydrophilic colloid. Examples of such ultraviolet absorbers include aryl group-substituted ones Benzotriazole compounds, 4-thiazolidone compounds, Benzophenone compounds, cinnamic acid ester compounds, Butadiene compounds, benzoxazole compounds and, moreover, ultraviolet rays absorbing compounds Polymers. These ultraviolet absorbers can be incorporated into the above-described hydrophilic colloid layer be fixed. In addition, the light-sensitive silver halide material can contain hydroquinone derivatives, Aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives and the like as anti-spotting agents.

The silver halide light-sensitive material of the present invention can make dispersions of water-insoluble or water-insoluble synthetic polymers in the photographic emulsion layer and other hydrophilic colloid layers thereof for

° 0 contain improvements in dimensional stability.

Synthetic polymers that can be used for this purpose include homo- and copolymers of Alkyl acrylate or methacrylate, alkoxyalkyl acrylate or methacrylate, glycidyl acrylate or methacrylate, acrylamide or methacrylamide, vinyl esters (e.g.

3?

-32-

Vinyl acetate), acrylonitrile, olefins, styrene, etc. and copolymers of the above monomers and acrylic acid, Methacrylic acid, οέ, β-unsaturated dicarboxylic acids, Hydroxyalkyl acrylate or methacrylate, sulfoalkyl acrylate or methacrylate, styrene sulfonic acid and the like.

In addition, the silver halide light-sensitive material Brighteners based on stilbene, triazine, oxazole, coumarin or the like. These brighteners can water soluble or water insoluble brighteners and can be used in the form of a disperser will.

A suitable support for making the silver halide material of the present invention includes films or films of semi-synthetic and synthetic polymers, such as cellulose nitrate, cellulose acetate, Cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate and a Barite layer or αί-olefin polymer (e.g. polyethylene, Polypropylene and an ethylene-butene copolymer) -coated or laminated paper. These supports can be colored with dyes and pigments.

they can also be colored black for the purpose of shielding light. The surface of the carrier is generally subjected to a subbing treatment to reduce the Adhesion of the photographic emulsion layer, etc.

to improve. Before or after the undercoat treatment, the surface of the carrier can undergo a corona discharge, be subjected to irradiation with ultraviolet rays, flame treatment, etc.

In the production of the light according to the invention

For sensitive silver halide material, the hydrophilic colloid layers, such as a photographic one Emulsion layer, on the support or another Layer can be applied by various known techniques, e.g. by dip coating, Roller coating, curtain coating and extrusion or extrusion coating. Advantageous can be found in the üS-PSs 2 681 294, 2 761.791 and 3,526,528 methods described can be used in accordance with the invention.

The silver halide light-sensitive material of the present invention is exposed using conventional techniques to obtain photographic images. For this Exposure can be any known light source (e.g. natural light (sunlight), a tungsten lamp, a fluorescent lamp, a mercury lamp, a xenon arc lamp, a carbon arc lamp, a xenon flash lamp and a cathode ray tube flying spot light are used will. The exposure time can of course vary in the range from 1/1000 s to 1 s, what is typically applied to photographic cameras. The exposure during shorter than 1/1000 s, for example an exposure of 1/10 s to

1/10 ° s using a xenon flash lamp or cathode ray tube can be used. In addition, exposure for longer than 1 s can be applied. If necessary, the spectral

^{ου The} composition of the light used for exposure can be controlled using a color filter «

The exposure can be done using a laser. Light generated by a fluofes-

-.3-r-

decorative material that is activated by electron beams, X-rays, / -ray, οι -ray and the like. Can be used.

In development processing of the invention Any known methods and processing solutions can be used for silver halide material as described, for example, in Research Disclosure No. 176, pp. 28 to 30, No. 17643. These photographs see Processing can be any photographic processing with the formation of silver images (black and white photographic Processing) and photographic processing to form dye images (a color photographic processing).

The Verarbeitungsteinperatur is usually selected in the range of 18 to 50 ⁰ C, can but lower than 18 ° C and higher than 50 ⁰ C to be.

Developers for use in black and white photographic processing can be known developing agents contain. Developing agents that can be used include dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), and aminophenols (e.g. N-methyl-p- ■ aminophenol). These developing agents can alone or used in combination with each other. In addition to the developing agent, the developer contains in general, other known additives such as a preservative, an alkaline agent, a

pH buffer and an antifoggant, and if necessary can he use a dissolution aid, a color-controlling or color-controlling agent, a development accelerator, a surface-active agent, a defoamer, a water softener

containing a curing agent, a hardener and a tackifier.

Photographic processing of the so-called "lith" type can be carried out on the photographic emulsion of the present invention be applied. The term "lith type development processing" / used herein is intended to indicate development processing in which to reproduce line photographic images or for the photographic reproduction of halftone images by means of dots, dihydroxybenzenes are usually used as developing agents and the development be carried out in a low concentration of sulfite ions. This processing becomes more precise described in Mason, Photographic Processing Chemistry, pp. 163 to 165 (1966).

° As a special type of development processing a method can be adopted in which the developing agent in the photosensitive Material is included, for example the emulsion layer and the development is carried out through

20th

Processing the light-sensitive material in an aqueous alkaline solution. 'Wicklermittel hydrophobic decision can be incorporated in the emulsion layer by various techniques, such as described in US-PS 2,739,890, GB-PS 813 253 and DE-1 ^J S Ί 547 763. DIG development processing, in combination with a silver salt stabilization _treatment using thiocyanic acid salts.

30th

Conventional fixing compositions can be used in the present invention. _T fixative which are useful include thiosulfuric acid salts and thiocyanic acid salts. In addition, organic sulfur compounds known to be a

35

Have fixing effect, used as a fixing agent

ι be. The fixing agent can be water-soluble aluminum salts included as hardener.

The formation of dye images can be carried out by conventional techniques, such as a negative-positive method, as described, for example, in the Journal of the Society of Motion Picture and Television Engineers, Volume 61, pp. 667 to 701 (1953), a color reversal method in which a negative silver image is formed by developing with a developer which is a black and white developing agent contains, and then at least one uniform exposure or another suitable one Is subjected to egg egg treatment, followed by color development, to obtain a Color positive image and a silver dye bleaching method, in which a photographic emulsion layer containing dye is imagewise exposed, then is developed to form a silver image and the silver image thus formed as a bleach catalyst is used to bleach the dye.

The color developer generally consists of an alkaline aqueous solution containing a color developing agent. Color developing agents which are useful are known primary aromatic Aminentwiek ler, such as phenylenediamines (for example 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diäthylamilin _/ 4-amino-

N-ethyl-N-ß-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-ß-hydroxyethylaniline, 3-methyl - 4-amino-N-ethyl-N-ß-methanesulfoamidoethylan.iline and 4 ~ amino-3-methyl-N-ethyl-N-ß-methoxyethylaniline). In addition, compounds such as those described in L.F-A ,. Mason, Photographic Processing

Chemistry, Focal Press, pp. 226-229 (1966), in U.S. Patents 2,193,015, 2,592,364, in JA-OS 64933/73 etc. can be used.

The color developer can also contain a pH buffer, an anti-development agent, an antifoggant etc. included. If desired, it can be a water softening agent, a preservative organic solvent, a development accelerator, a dye-forming coupler, a competing one or competitive coupler, a fogging agent, an auxiliary developer, a tackifier, a polycarboxylic acid-based chelating agent, an antioxidant and the like.

15th

Examples of such additives are described in Research Disclosure No. 17643 and in U.S. Patent 4 083 723, DE-OS 26 22 950 etc.

The photographic emulsion layer usually undergoes bleach processing after color release subjected. The bleaching processing can be carried out simultaneously with the fixing process or separately be performed. Bleaches that can be used include compounds of polyvalent metals, e.g. iron (III), cobalt (III), chromium (VI) and copper (II), peracids, quinones and nitroso compounds. For example can ferricyanide compounds / dichromic acid salts, organic complex salts of ferric iron

30th

and cobalt-III, such as complex salts of aminopolycarboxylic acids (e.g. ethylenediaminetetraacetic acid, Nitritotriacetic acid (nitrirotriacetic acid) and 1,3-diamino-2-propanol tetraacetic acid) or organic Acids, e.g. citric acid, tartaric acid and malic acid, persulphuric acid salts, permanganate salts,

-26-

Nitrosophenol and the like can be used. Of these

Compounds are potassium ferricyanide, iron III- ■ sodium ethylenediarain tetraacetate and ferric ammonium ethylenediamine tetraacetate particularly useful. Ethylenediamine-tetraacetic acid-iron-III-complex salts are useful both as an independent bleaching solution and in a combined bleaching and bleaching solution Fixing solution.

Accelerators, described in ÜS-PSen 3 042 520, can be added to the bleaching solution or bleach-fixing solution 3,241,966, JA Patent Publications 8506/70, 8836/70, etc., the thiol compounds described in the JA-OS 65732/78, and various other additions

15 can be added.

The silver halide photosensitive material used herein can be processed with a developer which is renewed and which is maintained according to methods described in JA-OSen 84636/76, 119934/77, 46732/78 _r 9626/79, 19741/79, 37731/79, 1048/81 and 1049/81 and in the JA patent application 102962/79.

The bleach-fix solution for use in: i processing of the light-sensitive silver halide material can be made according to the procedures described in JA-OSen 781/71, 49437/73, 18191/73, 145231/75, 18541/76, 19535/76, 144620/76 and in JA patent publication 23178/76

30 can be reproduced.

Some of the main advantages of the invention are:

• 1. At the stages of coating formation and drying a coating solution to form a hydrophilic colloid layer in the course of manufacture

-ΦΙ ■ position of a light-sensitive silver halide material occurs, even with rapid drying, for example when drying is carried out under conditions such that the water equilibrium content occurs in 3 minutes or less and in particular 2 minutes or less, no crosslinking occurs. Moreover, even if development is performed using an automatic developing device, there is no deterioration in image quality due to the adhesion of impurities composed mainly of oxidized products of developing agent to the surface of the photosensitive material.

2. A light-sensitive silver halide material is obtained, to which no other materials adhere sufficiently - and that free of Adhesion of impurities in the stage of

20 development processing is.

3. Because it is a silver halide photosensitive material having excellent physical properties (e.g. networking and prevention of

Adhesion) can achieve even if rapid drying is carried out, and more No impurities adhere to the manufacturing process during the processing stages and the development of the photosensitive material can be carried out very rapidly.

The following examples are provided for further explanation of the invention without limiting it.

-JkQ-

example 1

On a polyethylene double-laminated paper
were a first layer (bottom layer) up
ν 5th layer, as described in Table I, applied and various 6th layers (outermost
Layer) with different compositions like
in Table II were used to prepare various color photosensitive materials. 10

A coating composition for making the
first layer was made as follows.

100 g of a yellow coupler (^ 6) was dissolved in a mixture of 100 ml of dibutyl phthalate and 200 ml of ethyl acetate, and the solution was emulsified and
dispersed in 800 g of a 10% aqueous gelatin solution, the 80 ml of a 1% aqueous solution of

Contained sodium dodecylbenzene sulfonate. The so

Holding emulsion was then with 145Og

(70 g as Ag) of a blue-sensitive chlorobromide emulsion (Br: 80 MoI-S.) To achieve the desired Coating solution mixed. The other coating solutions containing the appropriate corresponding coupler

were held in the same manner as above

manufactured.

These coating solutions were _ft means of a Extru sions- or extrusion coating method applied and wash dried. It took about 1.5 minutes to reach the water equilibrium content.

Any photosensitive material so produced
was with blue light, green light and feces light (in
such a way that the color density obtained after

development was 1.0) exposed and then it was made with an automatic developing machine similar to those shown below Stages processed.

Processing stages

Temp. ( ⁰ C) Time (min)

Developer 33 3.5

Bleach-fix 33 .1 / 5

Water wash 38-35

The composition of the processing solution is in

given the following:

Developer 20

Benzyl alcohol 15th ml G Diethylene glycol 8th ml Ethylenediamine tetraacetic acid 5 G Sodium sulfite 2 «R anhydrous potassium carbonate 30th G Hydroxylamine sulfuric acid salt "3 G Potassium bromide 0.6

4-amino-N-ethyl-N- (ß-methane

sulfonamidoethyl) -m-toluidine-

2/3 sulfuric acid salt

monohydrate. 5 g

(adjusted to pH 10.20)

Water for the preparation of 1

Bleach-fix

Ethylenediamine tetraacetic acid 2 g iron (III) ethylenediamine

tetraacetate 40 g

Sodium sulfite 5 g

Ammonium thiosulfate 70 g

Water for making 1 1

The automatic developing device used for the above processing was a Fuji Color Sheet Roll Processor PSR-2O4O (commercial product of Fuji Film Co., Ltd.).

In addition, after a processing bath in the automatic developing device

commercially available color paper was introduced, processed for several days, and then each light-sensitive material was developed in a state in which a conveying roller of the automatic developing machine ² ^ tables was spotted.

After the development processing, the degree of soiling of the surface of the photosensitive Material due to the adhesion of impurities ^ gen established and the formation of crosslinks was determined visually. The results are shown in Table II.

-yr-

Tabel

5th layer (red-sensitive layer.)

.0

Content of 300 mg / m (calculated as Ag) of a silver

chlorobromide emulsion (Br: 50 mol%), 1000 mg / m

2 2

10 gelatin, 400 mg / m cyan coupler (No. 1) and 200 mg / m

a coupler solvent (No. 2).

4th layer (intermediate layer)

2 2

Content of 1200 mg / m gelatine, 1000 mg / m of an ultraviolet absorber (No. 3) and 250 mg / m of one Ultraviolet absorber solvent (No. 2).

3rd layer (green-sensitive layer)

Content of 290 mg / m (calculated as Ag) of a silver

2 chlorobromide emulsion (Br: 50 mol%), 1000 mg / m

2
Gelatin, 200 mg / m of a purple or magenta cup

25 lers (No. 4) and 200 mg / m of a coupler solvent (No. 5).

2nd layer (intermediate layer) 1000 mg / m ² gelatin

1st layer (blue-sensitive layer)

Content of 400 mg / m (calculated as Ag) of a silver

chlorobromide emulsion (Br: 80 mol%), 1200 mg / m

-44-- Π

Gelatin, 300 mg / m of a yellow coupler (No. 6)

2
and 150 mg / m 2 of a coupler solvent (No. 7).

carrier
Polyethylene double-laminated paper carrier

No. 1 coupler: No. 2 solvent; 2-1 ~ ιό - (2,4-di-tert-pentylphenoxy) -butanamido-4,6-dichloro-5-methylphenol

Dibutyl phthalate

No. 3 ultraviolet absorber: 2- (2-Hydroxy-3-sec-butyl-5-tert-butylphenyl) benzotriazole

No. 4 coupler:

No. 5 solvents! 1- (2,4,6-trichlorophenyl) -3- (2-chloro-5-tetradecanamido) anilino-2-pyrazolin-5-one

Tricresyl phosphate

No. 6 coupler:

No. 7 Solvent: -K ', - (2 _f 4-dioxo-5,5'"dimethyloxazolizin-3-yl) -2-ChIOr-S - /" ^ - (2 _f 4-di-tert-pentylphenoxy ) -butanamido_7-acetoanilide

Dioctyl butyl phosphate.

ω ο

οι

60

αϊ

Tabel

I.

Composition of the top layer No. 1 surface active
■ Medium +) 4 · · Saponin Results Contamination
degree during the
processing dto. iL I. '· 4 I t * ■ sample
No, gelatin Alkali-processed gelatin +) 2 B ⁺ S formation of
Networking not adherent dto. ^ V "! t
• I < 1 acid-processed gelatine +) 3 C ⁺ 6 educated not formed adhesive dto. O '..'. ': I.
t 4 t
i I 1 (I 2 dto. D + 7 dto. . dto. 3 dto. Ρ · * "8 . dto. dto. 4th dto. according to the invention
Connection No. 3 dto. not adherent 5 dto. according to the invention
Connection No. 2 dto. dto. 6th dto. dto. 7th according to the invention
dto. dto. 8th according to the invention
dto. dto 9

+) 1: contained the top layer in all samples

in addition, a sodium salt of 2,4-dichloro

- 5 2 6-hydroxy-S-triazine and 6.2 10 mol / m

the compound represented by the formula CH ₂ -COOCH ₂ CHCc ₂ H ₅ ) C ₄ H ₉

NaO ₃ S-CH-COOCH ₂ CHCC ₂ H ₅ ) C ₄ H ₉

+) 2: Isoelectric point: pH 5.0, 1.0 g / iaf

+) 3: Isoelectric point: pH 7.0, 1.0

: 6.2 10 ⁵ mol / m2

7 W / i)

IP-CH ₂ CHCH ₂ Of-CH ₂

OH ^

OH

^C 12 ^H 25 '

SO ₃ Na

^C 12 ^H 25- ° ^SO 3 ^Na

From Table II above, in the case of Sample 1, the alkali-processed gelatin as Binder used for the outermost layer was seen that during development processing no impurities adhered, but that cross-links due to rapid drying of the coating solution after their coating were determined. Thus, the silver halide light-sensitive material was the sample is unsuitable for practical use.

10

In addition, from samples 8 and 9, in which one Acid-processed gelatin was used in combination with the compounds of the invention, it can be seen that no crosslinking and no adhesion of impurities occurred during processing. They thus gave excellent performance.

In the foregoing, specific embodiments have been made the invention described; it is evident that those skilled in the art can make changes within the framework of the teaching shown can perform without departing from the scope of the invention.

25th 30th 35

Claims (16)

GRÜNECKER, KINKELDEY ₁ STOCKMAIR & * PARITNEK FUJI PHOTO FIIM CO., HDD. No. 210, Uakamura, Minami Ashigara-shi, Kanagawa, Japan 'PATENT LAWYERS »EUROPEAN PATENT ATTORNEYS A. GRÜNECKER, qpling. DR H. KINKELDEY, oipl-ing OR W STOCKMAIR. (»« »« - ,. «te ic OH K SCHUMANN, wm. "" »A P.H. JAKOB.ok-inu DR. G BEZOLD. oPLCnew W. MEISTER, apt. into the H. HILGERS, opuins DR. H. MEYER-PLATH, »pl-ins 8000 MÜNCHEN 22 MAXIMILIANSTRASSE 43 P 16 875 -60 / dg December 23, 1981 Process for developing photosensitive
silver halide photographic materials Claims e •1. Process for developing a photosensitive A silver halide material comprising a support and at least one light-sensitive silver halide emulsion layer on the support, a surface layer of the photosensitive Material containing acid processed gelatin as a binder, characterized in that in the presence of a Compound developed which is represented by Formula I. (D wherein R is a saturated or unsaturated aliphatic group having 7 to 22 carbon atoms or is a substituted aryl group; R _{1 is} a hydrogen atom or a methyl group; R "and R_ each represent an alkyl group or substituted one Is an alkyl group with 1 to 4 carbon atoms, R- and R, - each a hydrogen atom or a Represent an alkyl group having 1 to 4 carbon atoms; L has the meaning vc ^ - ^ GQNH-, -SO ₂ NH-, -Ο-, -S-, -CONH (CH ₂ ) j-0- , -SO ₂ NH (CH ₂ -P-NH- Oh or -0-CH ₀ CH-OH m is 0 or 1, η is 0, 1, 2 or 3, χ is 0, 1, 2 or 3, A is -C00 ~ or -SO ₃ "? and 1 is an integer of 2 or more. 2. The method according to claim 1, characterized in that that R is a saturated or unsaturated .Eiliphatic group having 8 to 15 carbon atoms is. 3. The method according to claim 1 or 2, characterized in that 1 is an integer from 2 to 5. 4. The method according to claim 1 or 3 _f, characterized in that R is a substituted aryl group represented by the formula Ia ¹⁵ // V ² ^ where R ^{1 is} saturated or unsaturated is an aliphatic group of 7 to 21 carbon atoms, y is O or 1, and ru is 1 or 2. 5. The method according to claim 1, 2, 3 or 4, characterized characterized in that the compound represented by the formula I is deposited in a hydrophilic colloid layer of the silver halide light-sensitive material is incorporated. 6. The method according to claim 5, characterized in that that the compound represented by the formula I is incorporated into a surface layer will. 7. The method according to claim 6, characterized in that the surface layer is a surface protective layer is. 8. The method according to claim 5, characterized / that the compound represented by the formula I in an amount of 1, Ox 1O ~. to 1, Ox 10 ~ - mol per g of binder is incorporated into the layer.
10 9. The method according to claim 6, characterized in that the process represented by the formula I —6 binding in an amount of 1.0 χ 10 to 1 , 0 χ 10 mol per g of binder is incorporated into the layer. 10. The method according to claim 7, characterized in that that the compound represented by the formula I in an amount of 1.0 χ 10 to 1, Ox 10 moles per g of binder incorporated into the layer is working. 11. The method according to claim 5, characterized in that that the compound represented by the formula 1 in an amount of 1.0 χ 10 to 1.0 χ -4 10 moles per g of binder is incorporated into the layer. 12. The method according to claim 6 _f, characterized in that ^ that the connection represented by the formula I dung in an amount of 1 _f 0 χ 10 to 1.0 χ -4 10 moles per g of binder is incorporated into the layer. 13. The method according to claim 7, characterized in that that represented by the formula I. Compound in an amount of 1, Ox 10 to -4
Ί, Ο χ 10 moles per gram of binder in the layer is incorporated. 14. The method according to claim 1, 2, 3 or 4, characterized in that that represented by the formula I. Connection in a development - * ■ "processing solution is incorporated into the
the development is carried out. 15. The method according to claim 14, characterized in that the compound is in the development processing solution incorporated in an amount of 0.1 to 10 g per liter of developing processing solution will. 16. The method according to claim 14, characterized net that connection in the development processing solution incorporated in an amount of 0.5 to 3 g per liter of developing processing solution will.