DE2151484A1 - Silver halide photographic light sensitive element - Google Patents

Description

Patent attorneys DR. E. WIEGAND DIPL-ING. W. NIEAAANN 2 1 5 1 A 8 A

DR. M. KOHLER DIPL-ING. C. GERNHARDT

MÖNCHEN HAMBURG TELEPHONE: 555 476 800OMONCHENIS, TELEGRAMS: KARPATENT NUSSBAUMSTRASSE 10

October 15, 1971 W 40 782/71

Fuji Photo Film Co., Ltd. Ashigara-Kamigun, Kanagawa (Japan)

Silver halide photographic photosensitive element

This invention relates to a silver halide photographic photosensitive element; in particular it relates to a light-sensitive silver halide photographic element having a panchromatic sensitivity to "flash exposure" in which case the term "flash exposure" is to be understood as defined below _o

In the information age, various systems have already been developed and studied to enable rapid delivery of information to reach. For example, there is a print facsimile system for quick delivery of a manuscript for a newspaper to a remote location, a high speed photo composition system for quick implementation in letters and a cathode ray tube propagation system for the display of information supplied by an electronic computer in the form of letters or images.

In the machines and tools for this quick information

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Delivery systems, in most cases, is a short exposure of less than 1/100,000 of a second, especially about 1/1,000,000 of a second is required. In recent years has been the demand for photosensitive elements for use in such machines and tools as above are mentioned particularly clearly. The light sources used in these machines and tools are the Xenon flash light source and the cathode ray tube light source in addition to a combination of a light source with a high Luminosity, such as a xenon arc lamp and a high-

ψ pressure mercury arc lamp with one. High speed lock. These light sources use, for example, a cathode ray tube with a special fluorescent material with a short afterglow time, commonly known as a flying point. For example, various fluorescent materials such as so-called ¹¹ PH "," P-16 "," P-22 "," P-22D "," P-24 ", etc. are used, and it is well known that under In these fluorescent materials, the P-11 has the maximum of the spectroscopic energy distribution of luminescence in a wavelength range of 460 nanometers (hereinafter abbreviated to "nm"), while the maximum of P-16 at a wavelength of 385 mn, the maximum of P-24 at 520 nm, the maxima of P-22D are at 525 nm and 638 nm and also at 450 nm, and the maxima of P-22 are at 675 nm and also at 620 nm. In light-sensitive elements in which the above-mentioned various fluorescent materials are used and which are suitable for recording an image on a cathode ray tube, it is necessary to give them an expanded panchromatic sensitivity at the end of the red region (around 700 nm) is emitted at a broad wavelength when a Xenon flash light source or a Xeiion arc light source is used. However, the light emitted from a light source forms an image on the photosensitive surface of a photosensitive member by an optical system consisting of a condenser lens, a negative matrix, a main lens, a

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Prism, a reflector and other special lenses or prisms for the conversion into characters or letters. As for the light reaching the photosensitive surface of the element, the light becomes a short wavelength absorbed much more than that of a wavelength by the above-mentioned optical system, so that a ratio of Light with a wavelength of ultraviolet light to blue light decreases, while a ratio of light a long one Wavelength increases »For this reason there is a spectral sensitization indispensable for increasing the sensitivity of the photosensitive element.

The afterglow period of the luminescence of the cathode ray tube described above is short, for example, about 1/10,000,000 second to 1/100,000 second, and with regard to a xenon flash lamp most used are those having a luminescence period of substantially the same short duration as in the above cathode ray tube exhibit. According to the invention, a brief exposure to these types of light sources as mentioned above is defined as "flash exposure" or "rapid exposure".

In the case of a high pressure mercury arc lamp, those are inside a range of $ 00 nm to 370 nm existing / bright lines and the lines of 405 µm and 436 nm ineffective similar to im Trap of the above xenon lamp while using the bright lines present in the wavelengths of 546 nm and 577 nm more effectively are than those in the previous case. Therefore a spectral sensitization is indispensable to the sensitivity of a photosensitive element.

An object of the present invention is to provide a photosensitive Indicate element that is spectrally sensitized towards the end of the red region, so that it is common in machines and tools for communicating information using the various light sources mentioned above,

209817/13

can be used and also has high sensitivity compared to flash exposure (rapid exposure).

The object of the present invention is achieved by using two kinds of carbocyanine dyes given below general formulas I and II of a silver halide photographic emulsion adds:

/ Z--, ■ A / ^Z 1 \ B ₁ -N- b »CH -O = GH-C- lP- R ₂ (^) _n _i ¹

where mean:

A is a lower alkyl group such as methyl and ethyl;

Z and Z _x ,, which are identical or different, each represent the non-metal atom groups required to complete a benzothiazole ring;

Ry and Rp each represent an alkyl group, e.g. methyl, ethyl, n-propyl, hydroxyalkyl (e.g. 2-hydroxyethyl and 4-hydroxybutyl), acetoxyalkyl (e.g. 2-acetoxyethyl and 3-acetoxypropyl), alkoxyalkyl (e.g. 2- Methoxyethyl and 4-butoxybutyl), alkyl with a carboxyl radical (e.g. 2-carboxyethyl, 3-carboxypropyl, 2- (2-carboxyethoxy) ethyl and p-carboxybenzyl), alkyl with a sulfo radical (e.g. 2-sulfoethyl, 3-sulfo- propyl, 3-sulfobutyl, 4-sulfobutyl, 2-hydroxy-1-sulfo-propyl, 2- (3-sulfc-propoxy) ethyl, 2-acetoxy-1-sulfo-propyl, 3-methoxy-2- (3- sulfo-propoxy) propyl, 2- [2- (3-sulfopropoxy) ethoxy] ethyl, 2-hydroxy-3- (3'-sulfo-propoxy) propyl, p-sulfobenzyl and p-sulfophenethyl), aralkyl (e.g. benzyl and phenylethyl) or allyl, and in this case at least one of the radicals R ^ and R _? Alkyl with a carboxyl group or alkyl with a sulpho group;

2η an anion, e.g. chloride, bromide, iodide, thiocyanate, Sulfonate, perchlorate, p-toluenesulfonate, methylsulfonate and ethyl sulfate; and

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η the integer 1 or 2 and in the event that the dye forms an inner salt, η = 1;

/ ^Z 2 \? ^{/ Z} § \ and R ₅ -NO = CH-C = CH-C = '# - R ^ ( ^X ₂ ⁰⁾ _m -1 II

where mean:

B is a lower alkyl group such as methyl and ethyl, or an aryl group such as phenyl;

Zp to complete a naphthothiazole or Naphthoselenazole ring's required non-metal atom group;

Z-, the non-metal atom group required to complete a naphthothiazole, benzthiazole, naphthoselenazole, or benzselenazole ring;

R, and R ^, the same radicals as the above-mentioned radicals R ^, and R ₂ , where at least one of the radicals R, and R ^ is alkyl with a carboxyl radical or alkyl with a Sulfor radical;

3K the same residues as above X ^; and

m is the integer 1 or 2 and in the event that the dye forms an inner salt, m = 1.

Examples of benzothiazole and benzselenazole rings starting with Z or Zp are completed are benzothiazole, 5-methylbenzthiazole, 5-chlorobenzothiazole, 5-methoxybenzothiazole, 5-bromobenzothiazole, 5 »6-dimethylbenzthiazole, 5-cyanobenzothiazole, 5-hydroxybenzthiazole, 5-rhenylbenzthiazole, 5-hydroxy-6-methylbenzthiazole, 5-lthoxy-6-methylbenzthiazole, 5-carboxybenzthiazole, benzselenazole, 5-methylbenzselenazole, 5-chlorobenzelenazole, 5-methoxybenzselenazole, 5 ~ ethoxybenzselenazole, 5-phenylbenzselenazole, 5,6-dimethylbenzselenazole and 5-hydroxybenzselenazole.

Examples of naphthothiazole and naphthoselenazole rings starting with Zp are completed are oc-naphthothiazole, ß-naphthothiazole, β, β-naphthothiazole, a-naphthoselenazole, ß-naphthoselenazole and

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β, β-naphthoselenazole. '

Examples of naphthothiazole, benzthiazole, naphthoselenazole and benzselenazole rings, which are completed with Z, are a-naphthothiazole, ß-naphthothiazole, β, β-naphthothiazole, benzthiazole, 5-methylbenzthiazole, 5-chlorobenzothiazole, 5-methoxybenzthiazole, 5-bromobenzothiazole, 5,6-dimethylbenzothiazole, 5-cyanobenzothiazole, 5-Phenylbenzthiazole, 5-Hydroxybenzthiazo 1, 5-hydroxy-6-methylbenzthiazole, 5-ethoxy-6-methylbenzthiazole, 5-carboxybenzthiazole, a-naphthoselenazole, ß-naphthoselenazole, β, β-naphthoselenazole, benzselenazole, 5-methylbenzselenazole, 5-chlorobenzelenazole, 5-methoxybenzselenazole, ^ - ^ enylbenzselenazole, 5j6-dimethylbenzselenazole and 5-hydroxybenzselenazole.

In the technical field of the production of photosensitive photοgraphischen Silberhalogenidelernenten it is known _t that when a silver halide emulsion, a sensitizing dye is added to "the wavelength range of the light sensitivity of the silver halide emulsion extended is (broadened), may be optically sensitized thereby the emulsion. For most photographic light-sensitive elements, there is a case where some kind of sensitizing dye is used to sensitize a desired spectrally sensitized wavelength region. In many cases, however, at least two kinds of sensitizing dyes are used in a combined state. In the combined use of sensitizing dyes as mentioned above, it is mostly the cases in which the spectral sensitivity of the combined sensitizing dyes is lower than that of the single dye.

Accordingly, it is considered to be one of the most notable problems in the field of spectral sensitization that a combination of sensitizing dyes with a supersensitizing Relationship to each other is found through the above

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215U8A - 7 -

does not mention the combination of sensitizing dyes is influenced for the worse or in which preferably the spectral sensitivity is further influenced by the combination is improved. However, between the chemical structures of a group of two dyes, one is supersensitizing Relationship with one another requires strict selectivity. Even assuming that obviously only one If there is little difference between the dyes in terms of their chemical structural formulas, the supersensitization function becomes markedly influenced in most cases by the above-mentioned difference. Accordingly, it becomes general considered difficult to obtain photographic effects from a chemical structural formula of each dye of the combination expect. In other words, the present invention relates to spectral sensitization in the Flash exposure or rapid exposure.

It is known that a common known method of increasing the spectral sensitivity is based on experimental results obtained by a longer exposure time than that of 1/1000 of a second was obtained. On the other hand, there is a difference in the spectral sensitization function established by the Flash exposure is obtained from the exposure of an ordinary period of time as heretofore known, and consequently surprising results will be obtained in most cases.

A photosensitive photographic element in which the dyes of the above general formulas I and II are used in combination, has a high spectral sensitivity in the flash exposure or rapid exposure, as described in the following examples, Das that is, it was found to have excellent supersensitization effects against flash exposure by a combined use of the dyes of formulas I and II were achieved.

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In the photosensitive photographic of the present invention Element - will have high sensitivity over a wide range of wavelengths achieved, which extends into the end of the red area and the discoloration by the sensitizing dyes of the photosensitive member after the treatment is small, and accordingly is that of the present invention silver halide photographic light-sensitive element particularly suitable for light-sensitive elements for the rapid handling of information,

Furthermore, it is also possible to increase the spectral sensitivity in a region with a shorter wavelength by are also used together with the combination of the sensitizing dyes of the formulas I and II as used in accordance with the invention are used, a sensitizing dye which sensitizes a region of a shorter wavelength. In particular may be a more sensitive and panchromatic silver halide photographic light sensitive element for flash exposure can be obtained by using a sensitizing dye having a shorter wavelength region sensitized, which is in a supersensitizing relationship to the sensitizing dye of formula I or II.

The so-called pseudocyanine, styryl and merocyanine dyes, for example, are suitable as sensitizing dyes for a shorter-wave range and the like and in particular a pseudocyanine dye of the general formula III given below, which causes a noticeable increase in sensitivity:

H-C

^R 6 209817/1341

where mean:

Y is hydrogen, hydroxyl, lower alkyl, e.g., methyl and ethyl, alkoxy such as methoxy and ethoxy, or a halogen atom such as chlorine and bromine;

Z ^ those to complete a 5- or 6-limbed heterocyclic ring required for a cyanine dye Non-metal atom group, examples of particularly suitable heterocyclic rings being: benzthiazole rings, such as benzthiazole, 5-hydroxybenzthiazole, 6-hydroxybenzthiazole, 5-methylbenzthiazole, 6-methylbenzthiazole, 5 »6-dimethylbenzothiazole, 5-chlorobenzothiazole, 5-methoxybenzothiazole, 5-bromobenzothiazole, 5-cyanobenzothiazole, 5-phenylbenzthiazole, 5-hydroxy-6-methylbenzthiazole, 5-A * thoxy-6-methyrbenzthiazole, 5-carboxybenzthiazole, 5-methoxycarbonylbenzthiazole and {j-ethoxycarbonylbensthiazole, Benzselenazole rings, such as benzselenazole, 5-methylbenzselenazole, 5-chlorobenzelenazole, 5-methoxybenzselenazole, 5-ethoxybenzselenazole, 5-phenylbenzselenazole, 5 »6-dimethylbenzselenazole and 5-hydroxybenzselenazole, or 2-quinoline rings, such as 2-quinoline, 6-methyl-2-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline and 6-chloro-2-quinoline;

_{Rc and Rg the same radicals as R 1} and R ^, where at least one of the radicals R 1 - and Rg is alkyl with a carboxyl radical or alkyl with a Sülfor radical;

Χ-, the same as X ^ ,; and

ρ is the integer 1 or 2, in the case where the dye forms an inner salt, ρ = 1.

Examples of sensitizing dyes of the general formula III are the following:

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III-l

215H84

H ₅ C

CH- <

CH, OH

C ₂ H ₅

(CH ₂ )

III-2

HO

Se

= CH- ^

OH

C ₂ H ₅ (CH ₂ )

III-3

; -CH-

III-4

- (CH ₂ ) (CH ₂ )

CH-

(CH ₂ ) N CH.

III-5

(CH ₂ ) ₃ SO H

3 \

209817/1341

The ratio of the sensitizing dye of the general formula I to the sensitizing dye of the general Formula II is not particularly limited, but it is particularly effective within a range of 9: 1 to 1: 9 » based on the weight ratio, and this ratio can be changed according to its purpose.

For the preparation of the photographic In emulsion, it is sufficient to add both kinds of dyes to a photographic emulsion by an ordinary method. In practice it is expedient to add the dyes to the emulsion in the form of a solution in a suitable solvent. One method of adding the sensitizing dye to the photographic emulsion is in the art of manufacture of the photographic emulsion is known and, in general, the sensitizing dye of the photographic emulsion can be used in In the form of a solution in a solvent such as water, methanol, ethanol, methyl cellosolve and the like. The concentration of the dye in the emulsion can be varied widely within a range of, for example 1 to 200 mg per kg of emulsion, depending on the desired effects.

For the silver halide photographic emulsion of the present invention Silver halides, such as silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, can be used will. These photographic silver halide emulsions can contain compounds of metals belonging to Group VIII of the Periodic System of elements (i.e. iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum) or gold compounds be added separately or together. The amount of the addition of these metal compounds is within a range

-6 - ^
ranging from 10 to 10 ^J mol per mol of silver halide and the metal compound (or metal compounds) can be added to the emulsion at the time of preparing the silver halide particles in preparing the silver halide emulsion, initiating ripening

20 98 17 / 1-3 A 1

be added to the emulsion or within these stages and, moreover, the metal compound can also be added to the emulsion at a point in time before the application of the same in the form of a layer and after the ripening of the same. aside from that According to the invention, additives such as are usually used can also be added to the emulsion in the customary manner such as chemical sensitizers, stabilizers, toners, hardeners, coating aids, antifoggants, Plasticizers, development accelerators, air antifoggants, Fluorescent brighteners and developers for activator development. Although a normal gelatin-silver halide emulsion according to the invention is used, photographic emulsions containing substances other than gelatin can also be used contain, such as a water-permeable colloid, water-soluble cellulose derivatives, polyvinyl alcohol, the others hydrophilic synthetic or natural resins or polymeric compounds with the sensitizing dyes of the invention can be sensitized to a sufficient extent. The emulsion used according to the invention can be applied to a suitable carrier, e.g. glass, a film made from a cellulose derivative, a synthetic resin film, a synthetic paper, a polyolefin-coated paper and baryta paper are applied in the usual way,

"Examples of dyes of the general formula I are given below indicated, but it should be noted that the dyes according to the invention are not limited to:

209817/13

Ι "Λ '

CHaCH ₂ COOH

1-3

I - *

CH ₃ 1

20 98 1 7/1341

-.14 -

1-7

CH ₃

> -CH ^a O-OH-

CH ₃ -CH = O-CH

CH ₂ COOH

'• (CH ₂ ) ₄ S0 ₃ ^e

(CHg) dCOOH

2 0 9817/1341

: S.

(cH ₂ ) ₃ so ₃ e

. 1- / 3

C ₂ H ₅ '

«0H-O» OH-

'(CH ₂ ) ₃ SO ₃ H

20981771341

Examples of dyes of the general formula II are given below indicated, but it should be noted that the dyes according to the invention are not limited to:

H-/

C ₂ K ₅

^ = CH-C ¹³ CH

(CH ₂ ) ₅ SO 3H

• 1- · '?; ■■

. ' CH ₂ CH ₂ COcP ''

r · ■ »· ■

■ f

O ₂ H ₅

209817/13

»Ν

'IC -

. ". .vr * C ₂ H ₅

Η-7

C ₂ H ₅

"CH-O = O H-

C ₂ H ₆

CH ₂ CH ₂ Ca-OH ₃

·, 6O ₃ H

0 9817-1341

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example 1

To a gold sensitized photographic emulsion containing a silver halide consisting of silver iodobromide (1.5 Mol% silver iodide), became a sensitizing dye and also a coating aid and a Harder added. The mixture thus obtained was applied to a cellulose triacetate support (amount of applied

Silver: 4.5 g / cm), for the production of test pieces. Of the The silver content was 1.3 g and the gelatin content was 70 g per kg of the emulsion obtained.

The specimens were measured using a Mark VII sensitometer, manufactured by EG & G Co, USA, through a Fuji filter SC-48 (the light with a wavelength of more than 500 mm passed) exposed for 1/100 or 1/1,000,000 second. The specimens exposed in this way were with a Developer of the following composition developed at a temperature of 20 ° C for 4 minutes:

Metol 2.2 S. anhydrous sodium sulfite 96 G Hydroquinone 8.8 G sodium (Monohydrate) 56 G Potassium bromide 5 G water ad 1 liter

The specimens developed in this way were also normally fixed, soaked and dried. The optical densities of the obtained Test pieces after drying were measured by a densitometer, and the results obtained are shown in FIG shown in the following Table I, in which a sensitivity value is expressed by a reciprocal number of an amount of light which a density of 0.3 was obtained. In these two

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play, the sensitivity value is a relative value, since the absolute amount of light that is transmitted through the The filter was not measured, but the relative value is sufficient in these examples because of the respective sensitivities with the same exposure time in the table correspond to each other.

209817/134

- 20 -

φ 7th ■ at Table I.
I.
* ... - 100
11.0 ■ Exposure before
1/1000000 sec. 8th game
No. 100 " 100
132 Ver
search
JlU . 100
115 " 233 1 ' .1 <130 100
• 120 2 Dye * [sensitivity to yellow j
• -. ■. .. """-'—-% (relative value) 100
lli5 210 ■ · 3 2 , added amount in ml / kg exposure
Emulsion), from 1/100 sec 130 • 100
128 • I-UC80)
11-60.0) 100
31.5 207 Ii ^r 3 1-1, (80) 11-60.0) 155 ■ 100 =
H ₄ O 5 ± -50.0)
11-6 (20) 100
125 192 6th Ii 1-50.0) 11-6 (20) 132 100
120 . 1-60.0)
: - 11-6 (20) 100 200 5 = 1-6 (1.0) 11-6 (20) • 100 100
75 1-70.0)
11-6 (50) 100
120 132 6th 1-7 (1.0) 11-6 (50) 125 ^! 100
112 1-8 (1.0)
ii-6 (5o) 100 7th 1-8 (1.0) 11-6 (50) '■ 130 ' . 100 1-11 (1.0)
11-6 (20) HiO 8th 1-11 (1.0) 11-6 (20) 1-7 (20) 1-11 (20)
11-9 (1.0) 1-7 (20) 1-11 (20) 11-9 (1.0) '. IJi (IiO) 11-6 (1.0) • IJiOiO) 11-6 (1.0) 111-5 (25)

(* The concentration of each dye was 2 χ 10 "^ mol / liter)

20 98 1-7./1 3 4 1

Claims (6)

Claims Silver halide photographic photosensitive element suitable for flash exposure and at least one layer of a silver halide photographic emulsion characterized in that the silver halide photographic emulsion has at least one sensitizing dye of the general formula I given below in combination with at least one sensitizing dye of the general formula II given below contains: -Z ^ A -Z: ^
R ₁ -NC = CH-O = GH-G = IP-R ₂ C ^) _n-1 (D where mean: A is a lower alkyl group, Z and Z ₁ , which may be the same or different, the non-metal atom groups required to complete a benzothiazole or benzselenazole ring, R ₁ and R ₂ each represent an alkyl group, where at least one of the radicals R ₁ and R _{2 is} alkyl with a carboxyl radical or alkyl with a Sulfor radical, X _{1 is} an anion and η is the integer 1 or 2 and for the palm ₅ that the sensitizing dye forms an inner salt, η - 1; UXXU. .ti - JM - O = Oil -O = Ort -O = Iv ^ - Jx ^, V- ^ p / λ \ * - * ·) which mean: B is a lower alkyl or aryl group, Z _{2 is} the non-metal atom group required to complete a naphthothiazole or naphthoselenazole ring, 209817/1341 ■ - 22 - R ₂ and the non-metal atom group required to complete a naphthothiazole, benzthiazole, naphthoselenazole or benzselenazole ring, R ^ the same radicals as R ^, and R ₂ , where at least one of the radicals R, and R ^ is alkyl with a carboxyl radical or alkyl with a Sulfor radical , the same remnants as x5jj and where m has the same meaning as n. 2. Silver halide photographic photosensitive element according to claim 1, characterized in that the photographic silver halide emulsion also has at least one sensitizing dye of the general formula III contains H-C (III) where mean: Rr and a hydrogen atom, a hydroxy group, a lower alkyl group, an alkoxy group or a halogen atom to complete a 5- or 6-membered heterocyclic ring non-metal atom group required for a cyanine dye, Rg the same radicals as R ,, and R ₂ , where at least one of the radicals R, - and R ^ is alkyl with a carboxyl radical or alkyl with a Sulfor radical,
the same remnants as X? and
where ρ has the same meaning as n. 3. Photosensitive photographic silver halide element according to claim 1, characterized in that the photographic 209817/1341 -23- 215U84 Silver halide emulsion also includes at least one compound of a metal from Group VIII of the Periodic Table of FIG Contains elements and / or a gold compound. 4-, Silver halide photographic light sensitive element according to claim 1, characterized in that the dye general formula I from the class of dyes 1-3 to 1-14 and the dye of the general formula II is selected from the class of the dyes II-1 to II-9. 5 · Silver halide photographic light-sensitive element according to claim 1, characterized in that the photographic silver halide emulsion also has at least one sensitizing dye from the group of pseudocyanine, styryl and merocyanine dyes contains. 6. Photosensitive photographic silver halide element according to claim 2, characterized in that the dye of general formula III is selected from the class of the dyes III-1 to III-5. 209817/1341