DE1472827A1 - Light-sensitive silver halide photographic emulsion - Google Patents

Description

Eastman Kodak Company, 3 ^ j3 State Street, Rochester, New York State, United States of America

Light-sensitive silver halide photographic emulsion

The invention relates to a photosensitive silver halide photographic emulsion containing a cationic Contains development accelerator.

It is known DAFL containing in developing certain photographic silver in pure hydroquinone and low sulphite developers images can be obtained with extremely> high contrast. This applies especially to fine-grained silver chloride, silver chloride bromide and silver chloride bromide iodide emulsions. The cause for this is probably a so-called, autocatalytic reaction, which is also referred to as infectious development and is probably caused by locally occurring high concentrations of developer reaction products.

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High contrast emulsions are found in the graphic arts Extensive use of technology for producing halftone images consisting of small halftone dots of various sizes. Particularly good results are achieved when a raster exposure over the entire area results in raster dots uniform size leads. Small differences in the speed of development due to the infectious development however, lead to undesirable changes in the point size, which results in differences in the overall density.

U.S. Patents 2,756,148, 2,691,586, and 3,030,209 typical high contrast silver halide emulsions are described.

Since the infectious development has caused in local increases in concentration of the reaction products occurring during the development process, there have been attempts to reach the desired high contrast by & fast developing. For this purpose, development accelerators, for example cationic compounds, were added to the emulsion in order to increase the development speed and improve the evenness during development. Photographic emulsions containing compounds of this type are described, for example, in U.S. Patents 2,423,5 * 9 and 2,288,226. Although some of these compounds accelerate development overall, their use often results in limited ranges in which development can be slowed down .

earner runs, so that no uniform results are achieved ' become minnes.

The invention was based on the object of producing fine-grain silver halide emulsions with high contrast, which have cationic development accelerators, which not only increase the development speed, but also a more uniform Ensure development.

The invention was based on the knowledge that as a development accelerator Quaternary ammonium salts with the desired properties, namely polymeric quaternary ammonium salts and not polymeric quaternary ammonium salts are suitable.

Accordingly, the photosensitive silver halide photographic emulsion is of the invention characterized in that it is a quaternary ammonium salt of the following as a development accelerator Formulas contains:

-CH- CH ₂ -

where mean:

R is an alkyl group and

X is an acid anion and wherein

η .has a value of about 1,000 to about 10,000

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2)

2 (X ")

in which: R is a group (CH ₂ ) _n H with η - 4 to 10,

Z has an optionally substituted 2 to 14 members

send group and X a SMureanion?

in which: R is a group - (CH ₀ ) H with η = 4 to 10,

c. η

R 'is an organic group with a chain of 8-20 carbon, Oxygen, nitrogen or sulfur atoms and

X is an acid anion.

In formula 1, R represents a preferably primary alkyl group with up to 18 carbon atoms, e.g. n-amyl, isoamyl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-nonyl, n- Itecyl or lauryl group, preferably a methyl, ethyl, n-propyl, n-butyl or an isobutyl group. X preferably represents an aryl sulfonic acid group (aryl sulfonate ^{anion), e.g. a benzenesulfonate anion, a 1} toluenesulfonate anion and the like, an alkyl sulfonic acid group, ie an alkyl sulfate anion, e.g. a methyl sulfate,

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represents ethyl sulfate, n-propyl sulfate or n-butyl sulfate anion. X can but also the meaning of an iodide, chloride or bromide anion or another acid anion.

The polymeric quaternary ammonium salts can be obtained by reacting the corresponding polymeric amines with an alkyl or aryl ester, the polymeric amine should have a molecular weight which has an inherent viscosity of 0.5 to 2.0, preferably 1.0 to 1.5 is equivalent to. Pk ⁷ The following relationship applies to the inherent viscosity:

Intrinsic viscosity «log e of the relative viscosity , concentration in (g / 100 ml)

the relation applies to the relative viscosity:

Relative viscosity = viscosity of the solution , viscosity of the solvent,
measured at 25 ° C

methyl alcohol being used as the solvent and the viscosity is measured in a viscometer in seconds.

In formula 2:

Z is an organic group, in particular alkylene having 2 to 14 members, which may consist of carbon atoms, oxygen and -Schwefelatomen, z _# example groups of the formulas:

- wläXVyH - a - OfIo. "V Uli, -, J

co * 2 ^v 2

0 0

- CHgCHSCHgCHgSCHgCH ₂ -, - CHgCNH (CH ₂ ) gNHCCHg -,

■? .

) ₁₂ -, - CH ₂ CH ₂ CCH ₂ CH ₂ -, - (CHg) g -,

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, X for example a halogen atom, a p-toluenesulfonate or Alkyl sulfonate group and the like. Other suitable divalent organic groups are e.g. B. in the United States patents 2 288 226, 2 944 851, 2 944 855 and 2 944 898.

Compounds similar to Formula 3 are described, for example, in the United States patent 2 271 623.

It has proven to be particularly advantageous to use the quaternary Ammonium salts together with one of the polyalkylene glycols described in US Pat. No. 2,886,437 in an emulsion to add a high contrast. This increases the contrast and improves the dot quality.

Further polyalkylene glycols, which correspond to the silver chloride bromide emulsions can be added to increase the sensitivity and contrast are disclosed in US Pat. No. 2,423 described. However, such additives often reduce the sensitivity. However, if a used according to the invention quaternary ammonium salt polyalkylene glycols containing silver chlorobromide emulsions is added, the sensitivity of the emulsion increases without reducing the contrast or uneven development occurs. Preferably, although not necessarily, the emulsions Polyalkylene glycols with a molecular weight of at least 400 are added, the alkylene groups of which have 2 to 4 carbon atoms

• Contain and the only hydrocarbon groups in Q-lykol

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represent. The alkylene glycols are preferred to the emulsion in a proportion of 2 to 2200 mg per mole of silver halide added.

Of the polyalkylene glycols, the alkylene oxide polymers have emerged Proven to be particularly advantageous.

For preparing the light-sensitive silver halide photographic emulsion of the invention is a fine grain silver halide emulsion having a silver chloride content of at least 60 mole percent is used, which can be prepared by the method described in U.S. Patent 2,756,148. Preferably the emulsion is 2 to 65O mg of a quaternary ammonium salt added per mole of silver halide.

The following examples are intended to illustrate the invention in more detail borrowed.

example 1

A fine-grain, an oleyl ether of a polyethylene glycol with A silver chloride bromide gelatin emulsion containing an average molecular weight of 18OO was divided into 4 parts, to which the following compounds have been added:

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Sample no.

1 comparison sample

2.55 milligrams of 2,5-dioxahexane pyridinium perchlorate per mole Silver halide

3 50 milligrams of poly-2-vinylpyridine, quartered with methyl p-toluenesulfonate per mole of silver halide

4,230 milligrams of acetonyl bispyridinium perchlorate per mole Silver halide

All 4 emulsions were on cellulose acetate carrier in one

2 Layer thickness of one mole of silver halide per 20.90J m (square feet). One strip of each film was screened for 2-3 minutes developed. (Kodak Super Line developer served as developer). The evenness of development was determined by that the dot area in percent was determined in different areas of the film strip. The following results were obtained:

2_ 2L_ 4_

St tire center - vertical

24 29 27

27 29 27

28 29 27 26 29 27 24 29 27

sample No. 1 Above 27 Above center 26th center 26th Below center il Below 1 sample No.

Center of the strip - horizontal

left margin 29 23 29 27

right margin 20 23 30 27

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Sample no. 1 Top left 29 Top right 29 Bottom left 29 Bottom right 29 Example 2

Stripes - diagonal

2? JO 27

23 "Ί0 27

24 30 28 24 29 27

The silver chlorobromide gelatin emulsion used in Example 1 was divided into 5 parts. The following connections were made to the parts added:

Sample no.

1 comparison sample

2.55 milligrams of 2,5-dioxahexane pyridinium perchlorate per mole Silver halide

3 35 milligrams of 2,5-dioxahexane-1,6-bis (2- (7-hydroxypropyl) -pyridinium perchlorate] per mole of silver halide

4 140 milligrams of 2,5-dioxahexane-1,6-his-C5- (N _J N ¹ -diethylcarbamyl) -pyridinium perchloride per mole of silver halide

5 125 milligrams of 2,5-dioxahexane-1,6-bis- | 2- (benzyl) -pyridinium perchlorate per mole of silver halide.

Coatings were produced from the emulsions according to the method described in Example 1, which were checked for their uniformity the development were evaluated. The results are shown in the following table.

Sample no. 1 2 3 4_ 5_ Strip center Perpendicular Above 15th 20th 17th 18th 18th Top center 16 20th 16 18th 19th center 15th 20th 17th 18th 20th Bottom middle 16 18th 18th 18th 20th Below 14th 15th 17th 17th 20th

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- ίο -

Sample no.

Left margin 16 center 15 Right margin 15

Sample no.

Upper left 16

Upper right l6

Lower left l6

Lower right l4

Strip center 15th - Horizontal 18th 18th 17th 17th 20th 20th 17th 18th 17th 19th 17th

Stripes - diagonal

18th
15th
17th
15th

18th
17th
16
15th

17th
17th
17th
17th

With alien 3> substituted cationic compounds (3, 4, 5) a greater evenness of development was achieved than with the more soluble unsubstituted quaternary ammonium salt (2).

Example 3

Further compounds were tested according to the procedure described in Example 1. The 2,5-dioxahexane-1,6-his (2-n-amylpyridinium perchlorate) gave excellent evenness of development when the dot area in% was determined.

The following compounds were not suitable for achieving uniform development:

Decame thy len-Qi, U; -di (oxyme thy l-o6-me thy 1) -pyridinium per chlorate,

7,18 ~ diazo-6,19-dioxotetracosane-1,2,4-bis (pyridinium perchlorate),

Nonadecamethylene-l, 19-bis- (pyridinium perchlorate),

3,6,9 * 12-tetraoxatetradecane-l, 14-bis-pyrldinium perchlorate and

3,6,9,12,15,18,21,24-octoxahexacosane-bis-pyridinium perchlorate.

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The photographic emulsions of the invention are developable.

The emulsions of the invention can be prepared by known methods be chemically sensitized. For this purpose, they can be made with natural active gelatin or with US patents 1,574,944, 1,623,499 and 2,410,689 be moved.

Chemical sensitization of the emulsions can also be carried out with those described in U.S. Patents 2,399,083 and 2,642,561 described gold salts. Potassium chloroaurite, potassium aurithiocyanate, Potassium chloroaurate, gold trichloride and 2-aurosulfobenzothiazolmethochlorld have proven to be particularly useful.

The emulsions can also be chemically combined with reducing compounds ζ, Β. with tin salts as described in U.S. Patent 2,487,850. Polyamines such as diethylenetriamine such as in U.S. Patent 2,518,698; polyamines such as spermine as described in U.S. Patent 2,521,925 or with bis (ß-aminoethyl) sulfide and its water-soluble Salts as described in U.S. Patent 2,521,926 will.

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The emulsions of the invention can also optically with cyanine or merocyanine dyes are sensitized. Such dyes are described in U.S. patents, for example

1,846,301; 1,846,302; 1,942,854; 1,990,507; 2 112 140; 2 165

2,493,747; 2,739,964; 2,493,748; 2,503,776; 2,519 ODl; 2,666,761; 2,734,900 and 2,739,147 and in British Patent 450 958 described.

The emulsions can also be stabilized with: mercury compounds as described in U.S. Patents 2,728,663 * 2,728,664 and 2,728,665, gold salts as described in U.S. Patents 2,597,856 and 2,597,915, triazoles as described in US Pat U.S. Patents 2,444,608, azaindenes as described in U.S. Patents 2,444,605, 2,444,606, 2,444,6O7, 2,450,397, 2,444,609, 2,713,541, 2,743,181, 2,716,062, 2,735 769, 2 756 147, 2 772 164, as well as by Birr in the journal for Wiss. Photographie, Volume 47, 1952, pages 2 to 28, disulfides as described in Belgian patent 569 317, quaternary benzo-azo compounds as described in U.S. Patents 2,131,038, polymethylene bis-benzothiazolium salts, such as in U.S. Patent 2,694,716, zinc and cadmium salssen as described in U.S. Patent 2,839,405, and carboxymethyl mercapto compounds as described in U.S. Patent 2,819,965.

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For the preparation of the silver halide emulsions can be used as dispersing Compounds for the silver halide gelatin or

.other colloidal substances, such as colloidal albumin, cellulose. derivatives or synthetic resins, for example polyvene, can be used. Examples include polyvinyl alcohol or the hydrolyzed polyvinyl acetates described in US Pat. No. 2,286,215, hydrolyzed cellulose esters such as the cellulose acetate described in US Pat -Patent 2 322 085 described water-soluble ethanolamine cellulose acetates, the ^{polyacrylamides or imide group-containing polyacrylamides described in the USA patent 2 5 2} H ^ 7 ^, the zein described in the USA patent 2 563 79I, which in the USA patent 2 768 15 ^ described vinyl alcohol polymers containing urethane carboxyl groups, the vinyl alcohol-vinylcyanoacetate mill polymers containing cyanoacetyl groups described in US Pat. No. 2,808,331, and those described in US Pat. No. 2,852,382, in the polymerization of a protein or a saturated acylated protein one containing a vinyl group polymers formed in monomers.

If appropriate, mixtures of two or more mutually compatible colloids can be used as dispersants in the preparation of silver halide emulsions. It is also possible to determine combinations of negative effects, sensitizers, hardening agents

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medium and the like. Can be used. In addition, you can the emulsions the usual Beschiohtungshilfsmittel and like. included. Among the high contrast emulsions here are silver halide emulsions with / '- fourths of at least 11 meant.

The emulsions of the invention develop particularly well with a p-dihydroxybenzene developer that is less than ° # ° 5 ß per liter of an aminohenzene developing agent and contains less than about 25 g per liter of dissociated sulphite,

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Claims (4)

Claims 1. Light-sensitive silver halide photographic emulsion containing at least 60 mol # silver chloride and containing a cationic Development accelerators which, after development in a hydrochloride silver halide developer with a low sulfite content, optionally in the presence of an alkylene oxide with a Molecular weight of at least 300, an i * <value of at least 11, characterized in that it is used as a development accelerator contains a quaternary ammonium salt of the following formulas: -CH- CH ₂ - 'η wherein: R is an alkyl group and X is an acid anion and wherein η has a value from about 1,000 to about 10,000; 2 (X ") where: R is a group ( with η - 4 to 10, 909813/1305 Z is an optionally substituted group having 2 to IH members and
X an SMureanionj where mean ^. R is a group - (CHg) _n H with η » h up to 10, R ^{1 is} an organic group with a chain of 8-20 atoms consisting of carbon, oxygen, nitrogen or sulfur atoms and X is an acid anion. 2. Photosensitive silver halide emulsion according to claim 1, characterized in that it contains 2 to 65Ο mg quaternHres ammonium · salt per MoI silver halide ^ nthMlt. 3. Photosensitive silver halide emulsion according to claims 1 and 2, characterized in that it additionally contains a polymeric alkylene oxide with a molecular weight of at least 300. 4. Photosensitive silver halide emulsion according to claims 1 up to 3, characterized by the fact that they are classified as quaternary ammonium 909813/1306 ORIGINAL INSPECTED 2,5-Dioxahexane-1 _# 6-bia- [2 - (> ^ hydroxypropyl) -pyridinium peroxide | 2,5-Dloxahexane-l _# 6-bla £ - (N, N ^l -DiMthylearbamyl) -pyrldlnlumperohloratJj 2,5-Dioxahexane-1,6-bls- {2- (benzyl) -pyridinium perohloratJj Aoetonyl-bia-pyrldinlumperohbrat ortr with methyl-p-toluene " sulfonate quaternary la ler tea contains poly-2-vinylpyrldine. 909813/1305 ORIGINAL