DE1813001A1 - Light-sensitive, photographic silver halide emulsion for microfilms - Google Patents

Description

T 46 460

Koniahiroku Photo Industry Co., Ltd., 1-10, 3-Chome, Nihonbaehi-Muro-machi, Chuo-ku, Tokyo / Japan

Light-sensitive photographic silver halide emulsion for microfilms

The present invention relates to sensitized, photosensitive, photographic silver halide emulsions for use in microfilms. In detail, this relates to Invention a photosensitive, photographic silver halide emulsion for microfilms, which is characterized according to the invention is that it contains in combination two or three compounds from the group of compounds of the following general formula I and a compound from the group of compounds of the following general formula II

Pl

N-C «CH-C = CH-Q =

I I v

R ₁ Ro R

Π 1

-G = N I

Ί-1

909829/1343

-2-

INSPECT «*

C = CH-CH =

(Cl)

wherein

_{5 f R} ^ _and ^ j _ewe ii _s stand for a lower alkyl radical or a carboxyalkyl, sulfoalkyl or suIfoalkoxyalky 1 group j R2 denotes a hydrogen atom or a lower alkyl group; R5 is an alkyl group, where at least one of the radicals R-] »R3» R ^ «^ d Rg must stand for a carboxyalkyl, sulfoalkyl or sulfoalkoxyalkyl group; Yj is a hydrogen atom, a chlorine atom, an alkyl group or an alkoxy group, X ₂ represents ^hydrogen or an alkyl group, wherein there is a methylene group if Y j represents a chlorine atom; Z represents a grouping of atoms which is capable, together with the adjacent nitrogen and carbon atoms, to form a heterocyclic ring such as a thiazoline-j benzothiazole, benzoselenazole ring, etc., see below; X is an anion 1st and 1, in and η each stand for the numbers 1 or 2.

Purely for long storage or for the reproduction of printed matter of various kinds including official documents, manuscripts, drawings, etc. is the photographic recording The use of microfilms is common knowledge 0 The color In such cases, however, the original to be photographed fluctuates over the entire range of the visible spectrum. Which he-

pi iiimpiiiiiPn " ** w

The photographic recordings mentioned should as a rule be made under a tungsten lamp, which is a variety of Has absorption lines in the long-wave range. Therefore, the sensitivity is that of an ordinary photographic one Halide silver emulsion is not sufficient when this emulsion is for a photographic light-sensitive material to be used for copying purposes such as microfilm archiving. It is required for for these purposes a conventional photographic silver halide emulsion which is panchromatically sensitized.

It is an object of the present invention to provide a photosensitive photographic silver halide emulsion to create an increased sensitivity over the entire range of the visible spectrum and especially in the long wave range and also provides good sharpness and is stable.

It has now surprisingly been found that a photosensitive, Photographic silver halide emulsion, which with two or three different compounds from the group of Compounds of the above general formula I in combination with a member of the compounds of the above general Formula II is offset, the improved sensitivity when used for microfilm archiving according to the Object of the invention has.

-4-

909829/1343

Typical suitable compounds of the general formulas I and II are listed below, for example, without this being thereby the scope of the invention is intended to be limited thereto.

-5-

9 0 9 8 2Γ9 / 13 4T

¹¹¹¹ I '"! Sii'iljPiliaaiiii'iiiNir ^1. Jj ι.-ΐϊΐ, ιΐίίΐΐΦΐιΐ!:! ·:?!; · ■»: ■. · Ψ. ■ «" ■ ■■:. ■. ■: "■ ■ ". ■ ■ ■ ■ _: i.-ni»! - :. ji .τ

Compounds of the general formula I

Number 1)

H ₂ C-

, C = CH-CH = CH- C'CH.

C ₂ H ₅ C ₂ H ₅

No. 2)

CH ₂ CH ₂ COOH

I ₂ CH ₂ COOH

No. (3)

C = CH-C = CH-C '

C ₂ H ₅ Br

No. (4)

^ C = CH-C = CH-C ^ N ^ 'CH, J ⁸ N

(CH ₂ J ₄ SO ₃ H

No. (5)

\ / ³

C = CH-C = CH-C

j CH ₃ φ | CH ₂ CH ₂ OH CH ₂ CH ₂ OH

No. (6)

C = CH Oo

(CH ₂ J ₂ OCH ₂ CH ₂ SO ₃ HM (C ₂ H ₅ J ₃ (CH ₂ J ₂ OCH ₂ CH ₂ SO ₃

909829/1343

Η »(7)

\ ⁶ / ^s

G = CH-C = CH-C ^

No. (8)

O = CH-C = CH-C

CH,

χι

LJf.

C ₂ H ₅

CH ₂ CH ₂ COOH

Br

No. (9)

Se Se

C = CH-C = CH-C

C ₂ H ₅

CH-z θ

C ₂ H ₅ Br

Νγ. (10)

.Se

.C = CH-C = CH-C.

n / ^% n

CH ₃ Θι

(CH ₂ J ₄ SO ₃ H (CH ₂ J ₄ SO ₃ '

Compounds of the general formula II

No. (11)

■ χ

C ₂ H ₅

—CH = GH-C *

C ₂ H ₅

IC ₂ H ₅ Cl Cl

G = CH-CH = CH-C '

C ₂ H ₅

.N

^ N

C ₂ H ₅ 909829/1343 -7-

No. (13)

C = CH-CH = CH-C

CH ₂ CH ₂ COOH

Br

The joint use of two or three compounds of the general formula I with a compound of the general formula II enables such a special spectral sensitization of a photosensitive silver halide emulsion to obtain, as it could never be observed by the sole application of the respective compounds. on In this way, the photographic emulsion can have a sufficient spectral sensitivity over the entire range of the visible Spectrum, so that this emulsion has extremely excellent properties for photographic reproduction. In addition, this emulsion shows when used good photographic properties for microfilms. Another advantage of the emulsion according to the invention is that that the distribution of the sensitivity maxima can be determined in an optimal way that the types and amounts of the compounds of the general formulas I and II can be varied. In addition, the sensitizer compounds cause according to Invention no adverse interaction with other photographic additives present in the emulsion can. A microfilm produced with the emulsion according to the invention is completely free from a reduction in the photographic

909829/1343

graphic properties (e.g. reduction in spectral sensitivity, etc.) during storage.

For the purposes of the present invention, all combinations of any two or three compounds of the general formula are I effective with any compound of the general formula II. However, as pointed out above, those are particular combinations are preferred in which at least one of the sensitizing dyes used is soluble has carboxyalkyl or sulfoalkyl-making substituents, because the color yellowing, which is usually observed after development, is due to the increased hydrophilicity Property can be remarkably degraded.

The addition of the compounds of the general formulas I and II to the photographic silver halide emulsion can be carried out according to conventional methods Procedure. For example, these compounds can be dissolved in a water-miscible organic solvent such as methanol, Ethanol, etc., to obtain a solution which is then added to the photographic emulsion. Alternatively, several solutions can be prepared in that the respective compounds in an organic Solvent are dissolved and then added to the photographic emulsion. The addition of the sensitizer compounds to a photographic emulsion can be carried out at any stage during the preparation of this emulsion. Ec is generally preferred that the addition immediately before loading

909829/1343

"! ■■ '· ■ ψ Γ"

The second ripening process ends. The total amount of sensitizer compounds that is used may vary depending on the kind of the photographic emulsion and the Types of sensitizer compounds vary. Usually, however, the amount is in the range of about 10 to 200 mg per Kilograms of photographic emulsion · Any kinds of light-sensitive silver halide emulsions according to present invention can be sensitized. Typical examples are silver chloride, silver bromide, silver iodobromide, Silver chlorobromide and silver chloroiodide emulsions. The photosensitive, sensitized according to the present invention Photographic silver halide emulsions can contain a gold, sulfur, reductive, or polyalkylene oxide sensitizer and other photographic additives known per se, such as stabilizers, coating auxiliaries, hardeners, etc. contain.

The present invention will now be explained with reference to the following examples, without the invention being restricted thereto shall be.

example 1

A silver chlorobromide solution for a copying material is prepared which contains 50 mol % of the emulsion. Immediately before the end of the second ripening process, the amounts of various compounds given in the table are in the form of 0.1 # strength methanolic solutions at elevated temperature

ι; - - ¹⁰ - ι

909829/1343

• ·

- 10 -

added. A support is then coated with this emulsion and dried.

The light-sensitive silver halide photographic film thus obtained (Microfilm) has good spectral sensitivity over the entire range of the visible spectrum and shows a particularly excellent spectral sensitivity in the long-wave range. This photographic film shows none any interactions due to the coexistence of the sensitizers and photographic additives, and he is free of any yellowing after developing. If this film is used for making copies, it will be a good one Reproduction obtained from an original showing spectral absorptions over the entire range of the visible spectrum shows, even when using a tungsten lamp as the light source.

The photographic film is exposed according to JIS method K-7609 and then for 4 minutes at? 0 ° C with a developer treated with the following composition »

Metol

Sodium bisulfite (anhydrous) hydroquinone

Sodium carbonate (monohydrate) potassium bromide

Water except for

1.0 g 75th Og 9 * 0 g

30.0 g 50 g 1.0 1

-11-

909829/1343

• ·

- 11 -

The results of measurements of photographic inventiveness and the yellowing (color staining) are summarized in Table 1. The test results are for comparison with photosensitive, photographic silver halide films produced by the sole use of the respective sensitizing dye e have been sensitized, also given in Table 1. The yellowing values are expressed than the parb density measured using a filter.

* or formation of veils

-12-

909829/1343

Table 1 Connections used lot
(ml) * Ver
am
application no. lot
(ml) * Ver
am
application no. Relative sensitivity white
light
(W) green
light
(G) red
light
(R) G / W R / W Color
stain ng that is added per kilogram of emulsion. ι
I. -tr I
Ver
am
application no. 100 _ _ _ 55 _ _ _ _ 0.02 OO
CaJ
O
O ( ¹ ) 100 - - - 75 45 25th 0.60 0.33 0.02 (6) 100 - - - 65 35 - 0.5 * - 0.03 (13) 30th (6) 50 (13) 105 75 50 0.72 0.48 0.02 ( 1) 50 (6) 100 (13) 110 85 60 0.77 0.55 0.02 (υ 100 - - - 40 - - - - 0.02 cc
C. (2) 100 - - - 85 55 35 0.65 0.41 0.03 cc
OO (5) 100 - - "- 75 40 - 0.53 - 0.03 cc (12) 30th (5) 50 (12) 100 75 50 0.75 0.50 0.02. (a (2) 50 (5) 100 (12) 105 75 60 O.71 0.57 0.02 Approx (2) * a 0.1 $ methanolic solution
I. lot
(ml) * _ - - 30th 30th - - - 30th 30th

• · a

• a · ·

- 13 -

From the above table it can be seen that the microfilms of the present invention greatly improved one photographic sensitivity to white light as compared to those films made using from only one of the compounds of the general formulas I and II were prepared. In addition, the films according to the invention have an improved ratio between G / Vf and R / W. It good spectral sensitivity is obtained over the entire range of the visible spectrum.

Example 2

The same silver chlorobroride emulsion as used in Example 1 is subjected to the second heat treatment with a gold sensitizer subject to obtain maximum sensitivity. Immediately before the end of this second ripening process portions of 1 kg each of this emulsion are made at high temperature in the amounts given in Table 2 various compounds in the form of their 0.1% methanolic compounds Solutions shifted. After finishing the second ripening process, the emulsion is made with an optimal amount of 4-Hydroxyr-6-methyl-1,3,3a, 7-tetrazainden added. The thus obtained Emulsion is applied to a support and then dried.

The light-sensitive, photographic halogen silver film (microfilm) has good spectral sensitivity over the entire range of the visible spectrum and is particularly excellent

-U-

909829/1343

with regard to its spectral sensitivity in the long-wave range. This photographic film shows none adverse effects due to the coexistence of the sensitizers and photographic additives and is completely free from color staining after developing. In addition, there is no deterioration in photographic properties observed even if the film is stored for a very long time. If this film for making copies is used, good reproductions of any originals can be obtained covering the entire range of the visible Spectrum have spectral absorptions, even when using a tungsten lamp as the light source.

The photographic film is exposed according to JIS method K-7609 and then with a developer in the same manner developed as described in Example 1. The photographic speed and fog are shown in Table 2. For comparison, the test results with photosensitive, photographic, silver halide films are also given, which have been sensitized by using only one of the sensitizing dyes

-15-

909829/134

Ver ^
am-
manure
No. • Ver
am
manure
No. Tabel 2 Ver
am
manure
No. Amount (ml)
from 0.1 jS
MeOH Lö
sung
adds to 1 kg
emulsion Ver
am
manure
No. ! narrow (ml) of 0.1 #
^ IeOH solution too
kg of emulsion I. t 1813001 ( 1) Amount (ml)
from 0.1 io
MeOH Lö
sung
adds to 1 kg
emulsion - - - - - VJl (4) 100 - Connections used mm - - - I. approx (10) 100 - Amount (ml)
from 0.1 i>
MeOH Lö
sung
adds to 1 kg
emulsion - - - - a
co (11) 100 - - - - - - CU
NJ (12) 100 - - - - - (D 100 (4) - (12) 30th - - OJ
OJ (D 30th (4) - (12) 30th - - ( 1) 50 (4) - (10) 60 (11) 20th (D 50 (4) 50 (10) 60 (11) 30th 50 100 40 40 attempt 1 2 3 4th 5 6th 7th 8th 9 I.

Table 2 continued Ver fresh sample
search Schlei-
he white
light green
light red
light 3 days at 55 ° C
stored white
light green
light red
light 3 days at $ 80 relative
Humidity and 50 C
stored white
light green
light red
light Max.
Sensi.
(m / u) I.
CTi
I. 1813001
-17- 1 0.02 55 - - Schlei
he 55 - - Schlei
he 55 - - 480 2 0.02 80 55 30th 0.02 85 55 30th 0.03 80 60 35 600 Relative sensitivity 3 0.02 80 50 35 0.02 80 55 35 0.02 80 55 35 620 4th 0.03 65 35 - 0.02 65 35 -, 0.02 65 30th - 540 5 0.02 70 40 - 0.04 70 35 - 0.03 70 40 - 540 CD
CD 6th 0.02 105 90 55. 0.03 110 85 55 0.02 105 90 55 600 CD
CO 7th 0.02 120 95 65 0.02 120 95 65 0.02 120 95 65 600 ■ Ό 8th 0.02 105 80 60 0.03 110 80 60 0.02 105 80 60 620 OJ 9 0.02 115 85 70 0.02 115 85 70 0.02 115 85 70 620 ω 0.02 0.02

• ··

• ·

- 17 -

From the table above it can be seen that the light-sensitive, Halide photographic photographic films according to the invention in terms of spectral sensitivity as compared with those films which are made using only one of the compounds of the general Formulas I and II were made. In addition, these films have good spectral sensitivity over the entire range of the visible spectrum. The durability of the films is satisfactory, since it is free from fog even after long storage, a decrease in photographic sensitivity etc. are.

In the accompanying drawing, FIG. 1 is the spectral sensitivity curve the silver chlorobromide emulsion used as the starting material in this example. Fig. 2 (I), (II) and (III) are the spectral sensitivity curves of the aforementioned Emulsion when each of the compounds No. (1), No. (4) and No. (12) was added. Fig. 3 is the Spectral sensitivity curve of the emulsion mentioned when the compounds No. (1), No. (4) and No. (12) are combined Contains added according to the present invention. The drawing clearly shows that a light-sensitive, Photographic silver halide emulsion according to the invention in terms of spectral sensitivity over the entire range of the visible spectrum in comparison with photographic emulsions containing only one of the compounds of the general Formulas I and II are offset, quite considerably

-18-

909829/1 3A 3

have improved properties.

Claims;

909829/13

Claims (7)

wherein R ₁ , R ^, R ^ and R ₆ each represent a lower alkyl group, a carboxyalkyl or a sulfoalkyl group, with at least one of the symbols R- |, R5, R4 and Rg ^for a carboxyalkyl, sulfoalkyl or Sulfalkoxyalkyl group; R _{2 is} a hydrogen atom or a lower alkyl group; R _{5 is} a lower alkyl group; Y represents hydrogen, chlorine, a lower alkoxy group; Y ₂ is hydrogen or a lower alkyl group, Y ₂ should be a methyl group when ^e i ⁿ Yj chlorine atom; Z is a group which, together with the neighboring nitrogen -20- gQgg29 / 1? /> 3 and carbon atoms is capable of forming a heterocyclic ring; X is an anion and 1, η and m stand for the number 1 or 2, respectively. 2. Halogen silver emulsion according to claim 1, characterized in that the combination of 3,3 * -diethyl-thiazolinocarbocyanine iodide, 3,3 ^l -sulfoethoxyethyl-9-methyl-thiacarbocyanintriethylamine and (3-carboxyethyl-5-raethoxybenzoxazole) - (1,3 diethyl 5,6-dichlorobenzimidazole) carbocyanine bromide, 3 · Halogene silver emulsion according to claim 1, characterized in that the combination of 3> 3 ^l -dicarboxyethyl-thiazolinocarbocyanine bromide, 3,3'-hydroxyethyl-9-methyl-thia-carbocyanin iodide and (3-ethyl-5-chloro-6 -methyl-benzoxazole) - (l-ethyl-3-sulfobutyl-5,6-dichlorobenzimidazole) -carbocyanine. 4. Halosilver emulsion according to claim 1, characterized in that the combination of 3 »3 ^f -diethyl-thiazolinocarbocyanine iodide, 3,3'-disulfobutyl-9-methyl-thia-carbocyanine iodide and (3-ethyl-5-chloro-6-methyl benzoxazole) - (1-ethyl-3-sulfobutyl-5,6-dichlorobenzimidazole) carbocyanine. 5. Halogen silver emulsion according to claim 1, characterized in that that the combination of 3,3'-diethyl thiazolino- -21- 909829/1343 - 21 - carbocyanine iodide, 3,3'-disulfobutyl-9-methyl-thia-carboeyanine iodide, 3 »3'-disulfobutyl-9-methyl-benzselenazolocarbocyanine and (3-ethyl-benzoxazole) - (1-ethyl-3-ethyl-5,6-dichlorobenzimidazole) -carbocyanineodide consists. 6. Microfilm consisting of a layer support and an emulsion applied thereon, characterized in that it an emulsion according to claims 1 to 5 contains. 7. Use of a combination of two or three compounds from the group of compounds of the general formula I and a compound from the group of compounds of the general formula II according to claims 1 to 5 as sensitizers for light-sensitive, photographic halogen silver emulsions for microfilms 909829/1343 -Vl- Blank page