DE1929039B2 - Photosensitive silver halide photographic emulsion - Google Patents

Description

L 0 (CH ₂ CH ₂ O) ₁ H

where R _{1 is} an alkyl group, R _{2 is} an alkyl group or a hydrogen atom and η is an integer from 1 to 100 in which these structural units have been polymerized to an average degree of polymerization of 2 to 10, in amounts between 0.01 and Contains 3.0 g per kilogram of silver halide emulsion.

The present invention relates to a photosensitive silver halide photographic emulsion comprising an alkylphenol-ethylene oxide addition polymer.

There are many methods of increasing photosensitivity photographic silver halide emulsions known. Typical such procedures are chemical sensitization process using sulfur compounds that lead to the formation of Silver sulfide are capable. It is also known to use suitable reducing substances or noble metal salts to use. Furthermore, it is generally known that the photosensitivity by combining the mentioned connections can be increased even further (cf. for example »The Theory of The Photographic Process ", 3rd edition [1967], pp. 113 to 117). as Another chemical sensitization method is also generally known as a method known under Use of polyalkylene oxide compounds with a molecular weight of at least 300 works. For example, in British Patent 805,826, photographic elements containing silver halides are referred to as elements Recording materials described the condensation products of ethylene oxide with phenolic Contain substances. However, these known recording materials are not sufficient Sensitivity, not satisfactory fog and / or especially not satisfactory: maximum density, which will be explained later on the basis of comparative experiments. All of these known However, sensitizers can only be added to the emulsions in limited quantities, and it if their amounts exceed a certain limit, disadvantages are caused by, for example photographic films made using such emulsions have a strong show increased fogging and insufficient stability when stored at elevated temperatures exhibit. In addition, such troubles may arise that the haze is too high has adopted and can no longer be controlled, even if the emulsions are anti-fogging agents had been inflicted.

The object of the invention is therefore to provide a light-sensitive photographic silver halide emulsion, which has improved sensitometric properties, in particular those made from it should

ίο recording materials through an increased Gamma, improved sensitivity and higher maximum density with good stability. Even there, the veil should remain almost unchanged if the storage of the recording material

at high temperatures.

Accordingly, the present invention provides a photosensitive silver halide photographic emulsion with an alkylphenol-ethylene oxide addition polymer, which is characterized by

The net is that they are the alkylphenol-ethylene oxide addition polymer as formaldehyde condensate with structural units of the formula

CH ₂ -

Q (CH ₂ CH ₂ O) _n H.

where R _{t is} an alkyl group, R _{2 is} an alkyl group or a hydrogen atom and η is an integer from 1 to 100 in which these structural units have been polymerized to an average degree of polymerization of 2 to 10, in amounts between 0.01 and Contains 3.0 g per kilogram of silver halide emulsion.

The compounds used according to the present invention cause a marked increase in the Sensitivity, maximum density and the gamma of what is achieved by using conventional polyalkylene oxide compounds to such an extent cannot be achieved.

In the polymers used according to the invention, the alkyl groups which are represented by R ₁ and which are bonded to the benzene nuclei of the structural units can be identical or different. These compounds can be prepared by any of the methods described in Kogyo Kagaku Zasshi (Magazine of Industrial Chemistry), Vol. 66,391 (1963), Abura Kagaku (Oil Chemistry), Vol. 12, 625 (1963) and Japanese Patent Publication 279 014 are published. In general, these compounds are viscous pasty, waxy or semi-solid resins and are soluble in water, acetone, alcohol and benzene.

Typical such compounds are listed below. According to the present invention however, useful compounds are not limited to these examples.

Connection 1

Compound with an average number of 9 structural units, produced by addition polymerization of p-cresol-formaldehyde resin with 1.5 mol of ethylene oxide per structural unit, ηΐ = 1.5808.

Connection 2

Compound with an average number of 5 structural units, produced by addition polymerization of p-cresol-formaldehyde resin with 8 moles of ethylene oxide per structural unit. »;; = 1.5199.

Connection 3

IO

Compound with an average number of 10 structural units, produced by addition polymerization of pn-nonylphenol-formaldehyde resin with 6 moles of ethylene oxide per structural unit. in: = 1.4928. is

Connection 4

Compound with an average number of 8 structural units, produced by addition polymerization of pn-octylphenol-formaldehyde resin with 15 mol of ethylene oxide per structural unit, n'i = 1.4917.

Connection 5

Compound having an average number of 5 structural units, prepared by addition polymerization of pn-octadecyl phenol-formaldehyde resin with 100 moles of ethylene oxide per structural unit, yo. Mp = 58-59 ° C.

Connection 6

Compound with an average number of 4 structural units, produced by addition polymerization of pn-nonylphenol-p-cresol-formaldehyde resin with 15 mol of ethylene oxide per structural unit. n'S = 1.4904.

Connection 7

Compound with an average number of 7 structural units, produced by addition polymerization of pn-nonylphenol-S ^ -di-n-nonylphenol-formaldehyde resin with 30 mol of ethylene oxide per structural unit. n ' _D ° = 1.4896.

The compounds used according to the present invention can be used at any time during the chemical ripening can be added. In general, however, it is preferred to use them after the chemical To add ripening. To do this, they are beforehand in water or in a water-miscible organic Solvent, such as methanol or ethanol, dissolved. The amount of compounds to add varies within the claimed range depending on the type of the invention Polymer or the composition of the silver halide.

The compounds used according to the present invention can be any type of silver halide emulsions such as e.g. B. silver chlorobromide or silver iodobromide emulsions are added. These emulsions are advantageously such that (^ means of noble metal or sulfur compounds. Rc duklionssensibilisatoren or sensitizers of the polyalkylene oxide type to be chemically sensitized. Also, they may be subjected to spectral sensitization or super sensitization using sensitizing dyes. Conveniently, they are stabilizers , Hardeners and surfactants.

The compounds used according to the present invention can not only be photographic Black and white emulsions, but also color photographic emulsions containing couplers are added will.

The present invention will now be explained in detail with reference to the following examples.

example 1

A highly sensitive silver halide emulsion prepared by the neutral boiling process for the production of negatives, containing 5 mol percent silver iodide and 95 mol percent silver bromide, was chemically ripened to maximum sensitivity _{using sodium thiosulfate as sulfur sensitizer and AuCl 3 as gold sensitizer.} The emulsion was then divided into portions of 100 g each. The compounds listed below and in Table 1 were then added to each portion:

Compounds 2, 3 and 4 according to the invention and A and B according to the British patent 805 826, listed below:

nC ₈ H ₁₇

0 (CH ₂ CH ₂ O) ₂₀ H.

Q (CH ₂ CH ₂ O) ₅ H

Then, per 100 g of emulsion, 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added as a stabilizer. Appropriate amounts of a hardener and a coating aid were then added to make emulsions ready for casting. These emulsions were applied evenly and under the same conditions to cellulose triacetate supports to produce sample films. The samples were then subjected to high temperatures and high humidity (manufactured and sold by Konishiroku Photo Industry Co., Ltd.) by means of a sensitometer KS-I at 160 Lux, exposed 5400 ⁰ K for 5 minutes and then at 20 ⁰ C with a Developer of the following composition developed:

N-methyl-p-aminophenol sulfate 3 g

Sodium sulfite (anhydrous) 50 g

Hydroquinone 6 g

Sodium carbonate (monohydrate) .... 29.5 g

Potassium bromide Ig

Topped up with water to 11

(The developer was asked to use
Water diluted 1: 1.)

Each sample was then examined sensitometrically, with those listed in Table I. Results were obtained.

Tabel

sample
No.

2
3
4th
5
6th
7th
8th
9
10
11th

Added
link

(2)
(2)
(3)
(3)
(4)
(4)
(A)
(A)
(B)
(B)
no

lot

(mg / 100 g
Emulsion)

60
100

60
100

60
100

60
100

60
100

Stored for 3 days under normal conditions

sensitivity

115 120 125 120 125 115 115 105 JOO 100 100

maximum density

2.00 1.95 2.22 2.20 2.15 2.20 1.91 1.94 1.85 1.82 1.85

veil

0.05 0.06 0.06 0.06 0.06 0.05 0.05 0.07 0.05 0.05 0.05 days stored at 55 C.

Sensitivity 115
120
125
125
120
115
115
110
105
98
103

The sensitivity is determined in accordance with JIS (Japanese Industrial Standard) method K-7604. For this purpose, the photographic recording material is exposed using an intensity scale sensitometer. The exposed film is developed as described. The photographic density is plotted against the amount of exposure log ₁₀ (lux · seconds). A point "A" is marked on the curve which corresponds to the exposure amount (EA) at which a photographic density (A) 0.1 above fog is obtained. Furthermore, a point "B" is marked on the curve, which corresponds to the value of the logarithmic exposure of point v> A "+ 1.5 units. The photographic density (B) corresponding to this amount of exposure (EA + 1.5 = EB) must be 0.75 to 0.90 above the photographic density of 0.1 above the fog (A) , ie B - A must be 0, 75 to 0.90. If this condition is met, the value of the exposure amount (EA) corresponding to the photographic density (A) at point "/ 1", ie 0.1 above fog, becomes the photographic speed according to the formula

Photographic sensitivity =

1.0 EA

maxi veil times density 0.06 2.05 0.06 2.00 0.07 2.25 0.07 2.22 0.07 2.20 0.06 2.20 0.06 1.88 0.08 1.90 0.05 1.88 0.06 1.84 0.06 1.88

Stored for 3 days at 50 "C and 80% relative humidity

sensitivity

120
115
120
125
125
120
110
105
100
100
100

maxi veil times density 0.06 2.00 0.07 1.95 0, U7 2.20 0.06 2.22 0.06 2.13 0.06 2.18 0.06 1.85 0.07 1.85 0.05 1.83 0.06 1.84 0.05 1.85

gamma

1.35 1.34 !, 41 1.38 L40 1.37 1.20 1.18 1.20 1.15 1.20

calculated. From the definition for point "B" of the sensitivity curve, it follows that the values for gamma or the density in the upper part of the curve correspond to the practical requirements. the The sensitivities determined in the process are given in the table as relative sensitivities, based on the sensitivity of sample No. 11.

It can be seen from Table 1 that according to the present invention, photosensitive photographic Materials are obtained which are improved in sensitivity, gamma and maximum density Have properties.

Example 2

The same high-sensitivity emulsion as in Example 1 was after the completion of the chemical Maturation divided into portions of 100 g each. The values given in Table 2 were given for each portion Connections added. Then 20 mg of 4-hydroxy-6-methyl-1,3,3 were added per 100 g of emulsion a, 7-tetrazainden added as a stabilizer. Then, appropriate amounts of a curing agent and a Coating aid added to make the emulsion ready for casting. This emulsion became uniform applied to a cellulose triacetate support and then dried. The samples thus obtained were subjected to a storage test at high temperature and high humidity, with the values shown in Table 2 collated results were obtained.

For comparison, a compound C of the formula was used to prepare a control sample

(C)

n-Co

-0 (CH ₂ CH ₂ O) ₂₀ H

(see British Patent 805,826) is used.

Tabel

sample

No.

Added
link

(1)
(5)
(7)
(C)
no

lot

Stored for 3 days under normal conditions

(mg / 100 g Sensation Emulsion) lich wedge 120 105 60 130 100 120 60 110 - 100

maximum density

1.97 2.20 2.10 1.92 1.90

veil

0.05 0.06 0.05 0.06 0.05 Stored at 55 ° C for 3 days

veil

0.06
0.07
0.06
0.07
0.06

Sensation maximum opportunity density 110 2.00 130 2.27 125 2.13 105 1.90 105 1.95

3 days at 50 ⁰ C and 80%

relative humidity

kept

veil

0.06 0.06 0.05 0.06 0.06

Sensation maximum opportunity density 105 2.00 135 2.23 120 2.12 110 1.87 100 1.90

929 039

The sensitivity was measured as described in Example 1.

It can be seen from Table 2 that according to the present invention, photosensitive photographic Materials are obtained, which after storage even under difficult conditions to a lower Tend to fog and show no decrease in sensitivity.

Example 3

A silver iodobromide color photographic emulsion containing 4 mole percent silver iodide was made with gold chloride and sodium thiosulfate chemically ripened. Immediately before the end of chemical ripening the emulsion was divided into portions of 100 g each. The compounds according to the present Invention were added to the individual portions in the amounts shown in Table 3. After the completion of the chemical ripening, a solution was added to each emulsion to make it dissolve at an elevated temperature of 1-hydroxy-2-N [«H2,4-di-tert-amyl-phenoxy-n-butyl] naphthamide as a protected cyan coupler in a mixture of di-n-butyl phthalate and ethyl acetate was. It was then dispersed in a gelatin solution using sodium alkylbenzenesulfonate. A hardener was then added and applied evenly to a cellulose triacetate carrier. It was then dried and each of the samples produced in this way was described in the same way as in Example 1, exposed and at 20 ° C for 10 minutes developed with a color developer of the following composition:

N-ethyl-N-fi-niethansulfonamido-

ethyl 3-methylaminoaniline sulfate .. 5.0 g

Sodium sulfite (anhydrous) 2.0 g

Sodium carbonate (monohydrate) .... 50 g

Potassium bromide 1.0 g

Benzyl alcohol 3.8 g

Sodium hydroxide 5.5 g

Topped up with water to 11

ίο Then each sample became the usual Subjected to treatments by stopping, fixing, washing and bleaching. Finally, in washed with running water for 20 minutes and then dried to obtain a cyan image.

The cyan image thus obtained became the sensitometric Subjected to investigation, whereby the results shown in Table 3 were obtained.

Table 3

sample

No.

Added
Connect
manure lot
(mg / 100 g
Emulsion) Sensation
opportunity gamma veil (3)
(3)
no 100
50 120
115
100 0.92
0.90
0.70 0.03
0.03
0.03

17th
18th
19th

The sensitivity was measured as described in Example 1.

From Table 3 it can be seen that the compounds according to the present invention are also advantageous coupler-containing emulsions can be added.

309 583 / 36.6

Claims (1)

I 929 039 Claim: Photosensitive fuiographic silver halide emulsion with an alkylphenol-ethylene oxide addition polymer, characterized in that that they are the alkylphenol-ethylene oxide addition polymer as formaldehyde condensate with structural units of the formula