DE1929039A1 - Light sensitive photographic silver halide emulsion - Google Patents

Description

Light-sensitive silver halide photographic emulsion

The present invention relates to a light-sensitive silver halide photographic emulsion which, in view of its Photosensitivity is improved. More particularly, the present invention relates to a photosensitive photographic Silver halide emulsion containing ethylene oxide addition polymers of .Alkylphenol-formaldehyde condensates.

Many methods have been proposed for increasing the photosensitivity of photosensitive silver halide emulsions been. Typical such processes are chemical " Sensitization process using sulfur compounds capable of forming silver sulfide. It is also known to use suitable reducing substances or noble metal salts. Furthermore, it is well known that the photosensitivity can be increased still further by a combination of the compounds mentioned. {See. for example "The Theory of The Photographic Process", 3rd Edition (1967), pp. 113-117J - Als Another Chemical Awareness-raising process is generally also a process

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. known that using polyalk / lenoxide compounds' works with a molecular weight of at least 500. However, all of these known sensitizers can only be used to a limited extent Amount are added to the emulsions, and if their amounts exceed a certain limit, there will be inconveniences caused by, for example, using the photographic films made from such emulsions show greatly increased fogging and have poor stability when stored at elevated temperatures. Furthermore Such troubles can arise that the haze has grown to a high level and is not controlled even if antifoggants have been added to the emulsions.

Taking this state of the art into account, extensive research now surprisingly found that when ethylene oxide addition polymers of alkylphenol-lOrmaldehyde condensates in the photographic Silver halide emulsion layers or in layers adjacent to these emulsion layers are incorporated, the films an increased photographic gamma, an improved effective Have sensitivity and maximum density with good stability and no fog even when the films are at high Temperatures have been stored.

The present invention accordingly provides a photosensitive, Photographic silver halide emulsion, which is characterized in that it is a jithylene oxide addition polymer of an alkylphenol-formaldehyde condensate.

The compounds used according to the present invention have, for example, "the advantageous effect that they the Silver halide emulsions do not fog after prolonged periods Increase time, the amount to be added is hardly increased and therefore they are easy to use, and the properties of

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photographic emulsions can improve. In particular, they show the salient effect that they have a noticeable Increasing the maximum density and gamma can result in what is made by using conventional polyalkylene oxide compounds cannot be achieved.

The ethylene oxide addition polymers of alkylene phenol-formaldehyde condensates, The genrJ.fi of the present invention can be used by the polymerization of structural units the general formula

0 (GH ₂ CH ₂ O) _n H.

where R _{1 is} an alkyl group, R _{2 is} an alicyl group or hydrogen and η is an integer from 1 to 100,

educated. Compounds in which these structural units have been polymerized to an average degree of polymerization in the range from «2 to 20 are preferred. In these polymers, 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, i) 91 (196 ^), Abura KagaKU (Oil Chemistry), Vol. 12, 625 (1965) and Japanese Patent Publication No. 279,014. In general, these compounds are viscous pasty, waxy or semi-solid resins, and they are soluble in water, acetone, alcohol, benzene and the like.

Typical such compounds are listed below. the Compounds useful for the purposes of the present invention.

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BAD ORJGiNAL

however, are not limited to these examples.

Compound 1: Compound made by addition polymerization of p-cresol -]? ormaldehyde resin with 1.5 mol, Ethylene oxide. n ^ ° 15808.

Compound 2: Compound made by addition polymerization of p-cresol-formaldehyde resin with 8 mol

Ethylene oxide. η ^ ^υ 15199

Compound 3: Compound made by addition polymerization of nonylphenol / ormaldehyde resin with 16 mol

on ethylene oxide. η £ ^υ 14928.

Compound 4: Compound produced by addition polymerization of octylphenol-formaldehyde resin with 15 mol of ethylene oxide. n ^ ^w 14917.

Compound 5: Compound produced by addition polymerization of p-octadecylphenol-I-malaldehyde resin with 100 mol of ethylene oxide. Fp 58-59 ⁰ C.

Compound 6: Compound made by addition polymerisation of nonylphenol-p-cresol-formaldehyde resin with 15 mol of ethylene oxide. n ^ 14904 connection 7: Connection produced by addition polymerisation of p-konylphenol-dinonylphenol-I-malaldehyde

20 resin with 30 mol of ethylene oxide. n ^ 14896.

The compounds used according to the present invention can be added at any time during the second ripening will. In general, however, it is preferred to add them after the second ripening is completed. To add the connections they are dissolved in water or a water-miscible organic solvent such as methanol or ethanol and the photographic emulsion layers or besides adjacent layers added. The amount of compounds to be added varies depending on the types of compounds or the light-sensitive substances used. As a rule, however, the tightness is in the range of 0.01 g

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to 3 g per kg of the silver halide emulsion.

The compounds used according to the present invention can be any type of silver halide emulsions such as silver chlorobromide, Silver iodobromide emulsions and the like Emulsions are added. These emulsions can be a gold sensitization, or chemical sensitization subjected to spectral sensitization or supersensitization using spectral sensitizing dyes have been. They can also contain various types of stabilizers, hardeners and / or surface-active agents Funds included.

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

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

example 1

An emulsion for a neutral process negative containing 5 mol $> silver iodide and 95 mol $ silver bromide was subjected to the second ripening process in order to obtain maximum sensitivity by means of a sulfur sensitizer and a gold sensitizer. The emulsion was then divided into portions of 100 g each. The compounds listed in Table 1 were then added to each portion. After adding an appropriate amount of saponin as a coating aid, each emulsion was uniformly coated on a cellulose triacetate film base under the same conditions to prepare a sample film. The samples were measured using a KS-1 sensitometer (manufactured and sold by Konishiroku Photo Industry Co., Ltd. ") at 160 lux,

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5400 ° K exposed and then developed for 5 minutes at 2O ⁰ G with a developer of the following composition:

Metol

- Hydroquinone anhydrous sodium sulfite

Sodium carbonate (monohydrate) potassium bromide
Water except for

3 g 50 g

6 g 29.5 g

1 g 1,000 ml

(For use, the developer was diluted 1: 1 with water).

Each sample was then examined sensitometrically, the results compiled in Table 1 being obtained became.

added
link Tabel. 1 Sensation
opportunity G-aiama maximum
density veil sample
No. . Connect 2 lot
mg / 100 g
emulsion 107 0.90 2.10 0.06 1 H 4 60 120 1.00 2.29. 0.06 2 »6 60 124 1.10 2.31 0.07 3 no to
gift 60 100 0.80 2.02 0.06 4th 0

In the table, the sensitivity is given as the relative sensitivity, with the sensitivity the sample No. 4, in which a compound according to the invention was not added, based on 100 became.

From Table 1 it can be seen that according to the present invention obtained photographic light-sensitive materials which have improved properties in terms of sensitivity, gamma and maximum density.

Example 2

The same highly sensitive emulsion as in Example 1

-7-

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became in portions after the end of the second ripening process divided by 1QO g each. The compounds indicated in Table 2 were added to each portion. Then 20 * ng of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added per 100 g of emulsion added as a stabilizer. Then, appropriate amounts of a curing agent and a coating aid were used added to make an emulsion. This emulsion was uniformly applied to a cellulose triacetate pilm support applied and then dried. The samples thus obtained were subjected to a high temperature storage test and high humidity, whereby the results shown in Table 2 were obtained.

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

0 (CH ₂ CH ₂ O) ₂₀ H.

(disclosed in British Patent Specification No. ÖO5, Ö26) was used.

The samples according to the present invention give excellent results light-sensitive photographic materials which, after storage, su an tend to be less foggy and show no decrease in sensitivity.

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added
link lot
(mg / 100 g
Emulsion) - £ ■ - maxi
times
density Tench: 3 days at 55 ^° C
kept maxi
times
density Schlei
he 3 days at 50 C and
80 $ relative air
humidity maxi
times
density Schlei
he 1929039 ■ Table 2 1.97 0.05 • Sens
lich
speed 2.00 0.06 Sensation
lich
speed 2.00 0.06 sample
No. Connect 1 120 3 days below normal
conditions stand
calmly 2.20 0.06 110 2.27 0.07 105 2.23 0.06 ti c 60 Sensation
lich
speed 2.10 0.05 130 2.13 0.06 135 2.12 0.05 Q ₀ ui η ₇ 100 105 1.92 0.06 125 1.90 0.07 120 1.87 0.06 6th control 60 130 1.90 0.05 105 1.95 0.06- 110 1.90 0.06 7th no to
gift - 120 105 100 In the table, the sensitivity is given as relative sensitivity, where
the sensitivity of sample No. 8 ¹ to which no compound was added,
was based on 100. 110 100. •

Example 3

A silver color photographic emulsion containing 4 moles of silver iodide was subjected to gold sensitization and sulfur sensitization to effect the second ripening, and immediately before the second ripening was completed, the emulsion was divided into 100 g portions. The compounds according to the present invention were added to the individual portions in the amounts given in Table 3; after the second ripening was complete, a solution was added to each emulsion which was obtained by dissolving at an elevated temperature of 1-hydroxy-2-ϊγ £ "/ (2,4-di-tert-amylphenoxy) butyl] naphthoamide as an internal gyan coupler was prepared in a mixture of di-N-butyl phthalate and ethyl acetate, followed by emulsification and dispersion in a gelatin solution using sodium alkylbenzenesulfonate offset emulsions with a hardener and uniformly cellulose triacetate film support coated on a. then was dried to obtain film samples were obtained. Each sample thus prepared was exposed in the same manner as in example 1, and then for 10 minutes of at 20 ⁰ O with a color developer the following composition:

N-Äf ^ hl-N-ß-methanesulfonamidoethyl-3-methylaminoaniline sulfate Sodium sulfite (anhydrous) sodium carbonate (monohydrate) Potassium bromide

Benzyl alcohol

Sodium hydroxide '

Water except for

Each sample was then subjected to the usual treatments by stopping, fixing, washing with. Water andt Bleaching. Finally, it was washed in running water for 20 minutes and then dried to obtain a cyan image became. The oyan image obtained in this way became the sensito-

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5.0 G 2.0 G 50 · G 1.0 G 5-5 G 1,000 ml

- ίο -

subject to metric examination, with the values given in Table 5 collated results were obtained.

added
link Table 5 Sensation
like-
.) speed gamma veil sample
No. Connect 5
It ti
no to
gift lot
(mg / 100
emulsion 120
115
100 0.92
0.90
0.70 0.05
0.05
0.05 9
10
11th 100
50

In the table, the sensitivity is expressed as a relative sensitivity indicated, the sensitivity of the sample obtained without adding a compound according to the invention was based on 100.

From this table it can be seen that the compounds according to the present invention are also advantageous and effective can be added to coupler-containing emulsions.

Claims;

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Claims (2)

Claims 1. Photosensitive, photographic silver halide emulsion, characterized in that it is a Ethylene oxide addition polymer from an alkylphenol-formaldehyde condensate contains. 2. Emulsion according to claim 1, characterized in that it additionally contains a color coupler. 3 emulsion according to claims 1-2, characterized in that that by means of precious metal sensitizers, sulfur sensitizers, reductive sensitizers or polyalkylene oxide type sensitizers. 4. Emulsion according to Claims 1-3 _5, characterized in that it additionally contains stabilizers, surface-active agents, coating auxiliaries and / or hardeners. 5 · Light-sensitive, color photographic silver halide element characterized by a film carrier and at least a coated thereon layer of an emulsion according to claims. 1-4. 909882/15