CS273673B1 - Method of orthochromatic supersensitized halogenosilver film preparation - Google Patents

Abstract

The solution concerns the preparation method of the orthochromatic super-sensitized silver haloid radiographic film, whose basic silver bromide-iodide emulsion with a various shape and size of emulsion grains is prepared by some of the usually used methods of emulsification as a single-jet, double-jet with the transition between the physical and chemical ageing by washing the emulsion strips or decantation of the separated solid phase AgHal, which is generally chemically sensitized, stabilized by general stabilizers and hardened by general hardening substances.

Description

SUMMARY OF THE INVENTION The present invention provides a process for the preparation of an orthochromatic supersensitized silver silver film for radioiodiagnostic imaging with output of image intensifiers X with a maximum emission of luminophores in the range of 530 to 560 nm and subsequent imaging with a quick-so-called spot-camera or , ultrasonography, and the like) with a spectral sensitization maximum of 550 to 5B0 nm with a spectral sensitization range of 590 to 600 nm.

The halo-silver radiodiagnostic material used up to now has been disclosed in foreign patents of the Federal Republic of Germany 2,344,565; 2,434. 171; 2,614,352; 2,487,868; NOR 114.022, 49.126; USA 3,823,136; 3,822.136; Jap 31 111 848; 81 111 1240; 81 111 849; 55 205 144; The GDR 201.208 shows a range of spectral sensitization in the range of 500 to 590 nm with a maximum sensitization at 550 to 580 nm using a combination of dye types such as dimethinmerocyanines + oxacarbocyanines, imidaindocarbocyanines + oxacarbocyanines, monomethincyanines + oxacarbocyanines, dimethinmerocyanines + imidaoxacarbocyanines, imidaoxacarbocyanines, imidathiacarbocyanines + oxathiacarbocyanines, nulamethinmerocyanines + imidathiacarbocyanines, some of which are difficult to obtain with low yields and often cause increased blackening without the exposure of the material, which is so unstable and deteriorates during the expiration period.

SUMMARY OF THE INVENTION The present invention relates to a process for the preparation of an orthochromatic supersensitized radiographic silver silver film comprising a bromide iodide silver emulsion containing 1.5 to 8 moles of AgJ and 92 to 98.5% AgBr of varying shape and size of emulsion microcrystals. It is prepared by one of the commonly used emulsification methods such as single-jet, with the transition between physical and chemical maturation, washing of emulsion noodles or decanting the separated solid phase of AgHal, commonly chemically sensitized, cured and stabilized with conventional curing agents and stabilizers. Spectral sensitization with a maximum of 550 to 580 nm is achieved by a combination of imidacarbocyanine and two oxacarbocyanine dyes with the supersensitizing effect of formulas I, II and III:

R 'i

= CK = CK = CH = C

\

where

R, R are saturated or unsaturated alkyl having a total carbon number of 1 to 3, carboxyalkyl having a total carbon number of 1 or 2, or sulfoalkyl having a total carbon number of 3 or 4; or phenyl

R ⁶ , R ⁷ represent hydrogen, halogen, CN or carboxyalkyl having a total number of carbon atoms of 1 to 4, and

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X = anion, (spectral sensitizers of formula I which are applied in the bromide iodine-silver emulsion used are given in Table 1),

where

9

R, R are saturated or unsaturated alkyl having 1 to 3 carbon atoms, carboxyalkyl having 1 or 2 carbon atoms, or sulfoalkyl having 3 or 4 carbon atoms, r10, rH being hydrogen, alkyl having total carbon atoms 1 or 2, halogen or alkoxy having a total number of carbon atoms of 1 or 2,

R is an alkyl group having a total number of carbon atoms of 1 or 2;

X '= anion (spectral sensitizers of the formula II, which are applied in the used bromide iodine-silver emulsion, are given in Table 2)

where R @ 13, R @ 14 are saturated or unsaturated alkyl having a total carbon number of 1 to 3, carboxyalkyl having a total carbon number of 1 or 2, or a sulfo group having a total carbon number of 3 or 4,

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R ¹⁵ , R ¹⁶ are phenyl,

R is an alkyl group having a total number of carbon atoms of 1 or 2;

X '= anion, (spectral sensitizers of formula III which are applied in the silver-bromide-silver emulsion used are shown in Table 3).

Combinations of spectral sensitizers guarantee the constant quality of the photographic material obtained, do not tend to create an increased veil without the exposure of the material and their preparation does not cause any problems. The prepared photomaterial has completely satisfactory parameters for radiodiagnostic imaging from image intensifiers X by imaging with quick-scan cameras or also for imaging methods with output on TV screen (in computed tomography, ultrasonography and the like) and is obtained from available raw materials.

Tab. 1 Sensitizers of the general formula I used

whose s. dyes R R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ R ⁷ X 1. c ₂ h ₅ c ₂ h ₅ ^C 2 ^H 5 ^C 2 ^H 5 Cl Cl H · H 3 2. ^ 2 ^ 5 ^C 2 ^H 5 c ₂ h ₅ ^C 2 ^H 5 Cl Cl Cl Cl 3 3. (CF3) jSO-jNa / CH2 / ₃ SO- c ₂ h ₅ c ₂ to ₅ Cl Cl Cl Cl betaine 4. / CH _2/4 S0 ₃ Na / CH ₂ / _t S0- ^C 2 ^H 5 ^C 2 ^H 5 Cl Cl Cl Cl betaine 5. / CH _2/3 S0 ₃ Na 'Vrt ^C 2 ^H 5 ^ 2 ^ 5 Cl Cl H H betaine 6. / CH _2/4 S0 ₃ Na /Cn/.SQ- ^C 2 ^H 5 ^ 2 ^ 5 Cl Cl H H betaine 7. / CH _2/4 SD ₃ On / CH _2/4 to; ^C 2 ^H 5 C ₂ ^H 5 Cl Cl Cl Cl betaine B. ^ 2 ^ 5 / CH _2/4 S0 ₃ ^ 2 ^ 5 ^C 2 ^ 5 Cl Cl Cl Cl betaine 9. ^ 2 ^ 5 / CH _2/4 S0 ₃ ^C 6 ^H 5 ^C 6 ^H 5 Cl Cl Cl Cl betaine

CS 273 673 B1 4

Tab. 2 Sensitizers of the general formula II used

no. dyes R ⁸ R ⁹ · • R ¹⁰ · Rll. R ¹ ? X ” la / CH _2/2 COO / CH _2/2 C00H Br Br ⁸ 2 ^R 5 betaine 2a / CH _2/3 S0 ₃ NH ₄ / CH _2/3 S0 ₃ Cl Cl ^C 2 ^H 5 betaine 3a / CH _2/4 S0 ₃ NH ₄ / CH _2/4 S0 Cl Cl ^C 2 ^H 5 betaine 4a / CH _2/4 SO ₃ c ₂ h ₅ Cl Cl CHj betaine 5a / CH _2/3 to ₃ ^C 2 ^H 5 Cl Cl ch ₃ betaine 6a / CH _2/3 S0 ₃ NH ₄ / CH _2/3 to ₃ Cl CH ₃ 0 ^C 2 ^H 5 betaine 7a / CH _2/3 S0 ₃ NH ₄ / CH _2/3 to ₃ Cl CH ₃ 0 ^C 2 ^H 5 betaine

Tab. 3 Sensitizers used according to general formula III no. dyes R ¹³ R ¹⁴ R ¹⁵ R ^lá R ¹⁷ X ' la c ₂ h ₅ / CH _2/3 S0 ₃ ^C 6 ^H 5 ^C 6 ^H 5 c ₂ h ₅ betaine 2b C ₂ ^h p / CH _2/4 S0 ₃ ^C 6 ^H 5 ^C 6 ^H 5 ^C 2 ^H 5 betaine 3b / CH _2/3 S0 ₃ NH ₄ / CH _2/3 SO ₃ ^C 6 ^H 5 ^C 6 ^H 5 ^C 2 ^H 5 betaine 4b / CH _2/3 S0 ₃ NH ₄ / CH _2/3 to ₃ ^C 6 ^H 5 ^C 6 ^H 5 ^C 2 ^H 5 betaine 5b / CH _{2/3 SO3 NH4} y CH _2/3 S0 ₃ Cl ^C 6 ^H 5 ^C 2 ^H 5 betaine žb / CH _{2/4 SO3 NH4} / CH _2/4 to ₃ Cl Cl ^C 6 ^H 5 betaine

Example 1

The photographic bromide iodine silver emulsion was prepared by single particle precipitation and solid phase separation using a gelatin derivative, having a mean particle size of 0.45 µm, a coefficient of variation of 25% and containing 97.3 mol% AgBr and 2.7 mol% Ag3 in the AgHal grain. This emulsion was chemically sensitized with sodium thiosulfate, ammonium sulfocyanide, gold sulfocyanide, and sodium benzenesulfinate at 55 ° C for 120 min. Chemical maturation was terminated with sta5

CS 273 673 B1 by 4-oxo-6-methyl-1,2,4-triazolo [2,3a] pyrimidine bilization. 20 mg dyes were used for spectral sensitization. 6. 3 + 20 mg dyes. £. 3a + 20 mg dye. No. 3b per kg of emulsion.

The emulsion was further cured with 2-hydroxy-4,6-dichloro-1,3,5-triazine sodium and conventional wetting agents were added prior to coating. The glaze emulsion thus prepared contained 65 g Ag / kg and 60 g gelatin / kg. The emulsion was then applied to a cellulose triacetate-based support and provided with a gelatin protective coating. The deposit of silver on the substrate was 5.0 - 0.2 g / m ² .

Example 2

A photographic emulsion was prepared in the same manner as in Example 1, except that 20 mg of dyes were used for its spectral sensitization. No. 4 + 20 mg dyes. No. 6a + 20 mg dye. No. 3b per kg of emulsion.

Example 3

A photographic emulsion was prepared in the same manner as in Example 1, except that 20 mg of dyes were used for its spectral sensitization. No. 6 + 20 mg of color. No. 6a + 20 mg dye. No. 6b per kg of emulsion.

Individual tests were exposed to the FSR 41 sensitometer at a color temperature of 5,400 K with an exposure time of 0.05 s, developed in the developer at 20 ° C for 5 min in a developing machine with a rocking motion of the sample, and stabilized in an acid fixer at 20 ° C for 20 min. After washing in running water and drying, the sensitograms were measured on a Meodcnzi 7RD 04 densitometer,

The developer used contains a villa of total volume

3.5 g methanol g sodium sulfite 9 g hydroquinone g sodium carbonate

3.5 g of potassium bromide

The fixer used contains a villa of a total volume

250 g sodium thiosulfate crystals.

g sodium disulphite

The obtained sensitometric values of the optical density of the veil D, the slope G and the sensitivity S _Q gg are given in Tab. 4 (the Y index indicates exposure values after the yellow filter ZS-1B from the sensitometer accessory, the relative sensitivity of rel. S is related to Example 1).

Tab. 4

Example no. ° o G G ^{Y S} 0.85 Y rel.50,85 1. 0.07 3.0 2.8 290 1.0 2. 0.06 3.1 2.9 350 1,2 3. 0.07 2.8 2.7 320 1.1

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Claims (1)

SUBJECT OF THE INVENTION A process for the preparation of an orthochromatic supersensitized halogen silver film whose basic bromide iodine-silver emulsion of various shape and size of emulsion grains is prepared by one of the commonly used emulsification methods such as single-jet or double-jet with physical / chemical maturation commonly chemically sensitized with gold and sulfur compounds, stabilized with conventional stabilizers and cured with conventional hardeners, characterized in that the bromide iodine-silver emulsion containing 1.5 to 8 mol% AgJ and 92 to 98.5 mol% AgBr in the AgHal grain is spectrally sensitized by addition a combination of an imidacarbocyanine dye with two α-carbocyanine dyes having the supersensitizing effect of formulas I, II ,. III: x '(I) where R ¹ , R ¹ are saturated or unsaturated alkyl having a total carbon number of 1 to 3, carboxyalkyl having a total carbon number of 1 or 2, or sulfoalkyl having a total carbon number of 3 or 4, R ² , R ³ are saturated or unsaturated alkyl having a total number of carbon atoms of 1 to 3, or phenyl, R ⁴ , R ⁵ , R ⁶ , R ⁷ are hydrogen, halogen, nitrile or carboxyalkyl having a total number of carbon atoms of 1 to 4; and X '= anion 7 CS 273 673 Bl where o g R, R are saturated or unsaturated alkyl having a total carbon number of 1 to 3, carboxyalkyl having a total carbon number of 1 or 2, or sulfoalkyl having a total carbon number of 3 or 4, R ^10, R ¹¹ represent a hydrogen atom, an alkyl group having a total carbon number of 1 or 2, halogen, or alkoxy group having a total carbon number of 1 or 2, R is alkyl having a total number of carbon atoms of 1 or 2, and X 'represents = aninon where ^ 13 ^ 14 mean aikyigkupj _nu saturated or unsaturated, with a total carbon number of 1 to 3, a carboxyalkyl having a total carbon number of 1 or 2 or a sulfo group having a total carbon number of 3 or 4 15 16 R, R are phenyl, R7 ^-7 is alkyl having a total number of carbon atoms of 1 or 2; X 'is an anion