DE2116259C3 - Spectrally sensitized photographic recording material - Google Patents

Description

A-SO ₃ -

B-SO ₃ -

wherein Z ₁ and Z _{2 are} a sulfur atom or a selenium atom, \ a substituent. VV a hydrogen aiom. a halogen atom, a lower alkyl group. Alko.xygruppe, hydroxyl group or aryl group. A and B are a polymethylene or alkylpoK methylene group, M ^{+ is} a hydrogen cation. mean a metal cation or an organic amine cation. and from at least one nucleus-substituted ms-ethyl-substituted benzothiazole or benzoselenazole trimethine vanine of the formula

(U!

wherein Z ₃ and Z _{4 represent} a sulfur or selenium atom. R ₂ and R _{3 represent} a lower alkyl group or substituted alkyl group. X ~ is an anion, η the number 0 or 1, where η has the value 0. if the dye forms an inner salt, characterized in that the emulsion layer contains those ring-substituted, ms-ethyl-substituted trimethine cyanines of the formula I in which the substituent Y is an optionally esterified carboxyl group R ₁ OOC-, where R _{1 is} a hydrogen atom or a lower alkyl group represents.

2. Photographic recording material according to claim I. characterized by the content of at least one spectral sensitizer dye of the formula I. in which the radicals Z and Z ₂ consist of a sulfur atom. R _{1 represents} a hydrogen atom or a methyl group. W is a chlorine atom. a phenyl group or methyl group. exist and at least one spectral sensitizer dye of the general formula II.

3. Photographic recording material according to claim I or 2. characterized in that the substituted alkyl group corresponding to the radicals R ₂ or R _{1 of} the formula II consists of an alkyl group which contains a sulfo group, an alkyl group. which contains a carboxy radical, or an allyl group.

Photographic silver halide emulsions, ie for the red spectral region with a mixture au at least two different ms-methylsubstituiei ten Benzthiazol- or Benzselenazoltrimethincyanine are spectrally sensitized, one of which is a kerr unsubstituted ms-methyl-substituted Trimethiri cyunin and the other an ms-ethylsubstituierie> Nuclear-substituted trimethyncyinine is known from French patent 1,497,142.

, 0 In the technique of making voi photograph] See emulsions there is great interest in finding a supersensitive-based combination nation of sensitizer mixtures for the Sensibilj in the red area, especially between 62:

and 665 nm. The supersensitizing Miscbunj according to the French patent specification I 497 142 is not yet satisfactory in terms of de effective supersensitization of the red spectral range and especially of the RereiY! »s from 625 to:

665 nm.

The object of the invention is therefore the creation of Sensibilis.itonni.schungen that in a photograph see recording material a panchromatic covering the green and red spectral range Sensitization of the highest red sensitivity mil provide a sensitization maximum, in particular in the range between 625 and 665 µm.

Panchromatic, the green and red spectral range Covering sensitizations are necessary for certain black-and-white materials.

The object of the invention is based on a photographic recording material with a light-sensitive silver halide emulsion layer applied to a support, which is characterized by a content of a sensitizer mixture is spectrally sensitized. which consists of at least one Nuclear-substituted, ms-ethyl-substituted benzothiazole and or benzoselenazole trimeline cyanine of the formula

Z, V "s

C ₂ H ₅

! I> - ■ CH = C- CH- (Jl 1

M ⁺

A-SO,

B-SOf

wherein Z ₁ and Z _{2 are} a sulfur atom or a sulfur atom, Y is a substituent. W is a hydrogen atom, a halogen atom, a lower alkyl group, an alkoxy group,

Hydroxy group or aryl group, A and B a pyIymethylene or alkylpolymethylene group. M ⁺ mean a hydrogen cation, a metal cation or an organic amine cation, and of at least one nucleus-substituted. ms-ethyl-substituted benzothiazole or benzoselenazole trimethine cyanine of the formula

R,

--CH --- = C - CH

R,

wherein Z, and Z _{4 is} a sulfur or sclen atom. R ₂ and R, a lower alkyl group or substituted alkyl group c. X is an anion. / 1 denotes the number O or I, where / 1 has the value O. when the dye is one

Inner Sal / forms, and is characterized in that the emulsion layer contains those nucleus-substituted, ns-ethyl-substituted trimethine cyanines of the formula I, in which the substituent Y is a given • Uj ₁ esterified carboxyl group R, OOC-, where 5 \ is a hydrogen atom or represents a lower alkyl group.

^r in the above formula can e.g. B. W is a methyl or ethyl group, a chlorine atom or bromine atom, a methoxy or ethoxy group or a phenyl group; the radicals A and B can each represent, for example, an ethylene, trimethylene or tetramethylene group or a methyltrimethylene group, and M ⁺ can represent, for example, potassium, sodium, triethylammonium, pyridinium or an S-benzylthiouronium potassium.

Furthermore, the radicals R ₂ and R _{3 can be} methyl, ethyl. Propyl or butyl group, and preferably an ethyl group, or a substituted alkyl group with a sulphate. ? .. B. one _; -Sulfnpropyl-. v-Sulfobim ν 1-- Λ-Sulfobui}! group, an alkyl group with a carboxy structure. for example a; -Carboxyprop>! ure group. an Alhluruppe. for example a

H ₃ COOC

Be vinylmethyl group; X can, for example, be a halogen ion, perchlorates, thiocyanate ion, p-toluenesulfonution, Ben / olsulfonatiane, ethylsulfalion or methylsulfate ion being.

As mentioned above, a particular feature of the invention resides in the supersensitization of photographic emulsions in the red spectral region by using two types of cyanine dyes according to the above general formulas I and II, wherein according to general formula I the cyanine dye is one having sulfoalkyl groups in the 3,3'-positions and with COOH or COOCH ₃ in the 5-position benzoxazole or benzoselenazole ring and a suitable amount of the indicated by the general formula II. Cyanine dyes in combination with Dye I is used. Furthermore, it is possible to jointly use a spectral sensitizer to increase the sensitivity in the green spectral range, for example a 2'-thia cyanine or a 2,2-cyanine. Typical spectral sensitizers which are useful in the context of the invention are given below.

CH ₅

J "

-C-C

ICHj) ₃ SO ₃ NH (C ₂ Hs) ₃ (CH ₂ I ₃ SO,

K,

H ₃ COOC

HOOC

HOOC

HOOC

ii, cooc

CJl,

> -CH = --- C-CH = <

(CH ₂ ) ₃ SO ₃ NH (C ₂ H ₅ } ₃

C ₂ H ₅
-CH = C-CH = - /

(CHj) ₃ SO.,

Cl

(CHj) ₃ SO ₃ HN (C ₁ H ₅ ).,
S.

CH

(CH ₂ )., 3O ₃

r ir

CH C CH

(CH ₂ USO ₃ S

OCH ₃
(CH ₂ ) ₃ SO, HN (C ₂ H _S

C ₂ W, _s

I / γ

ClI C (H < H

(CHj) ₃ SO ₃ ν y

(CHj) ₁ SO ₃ NH (C ₂ MO.,

CU, I > (Il C CU

CJI ₅

N
(Ml,

NI

lh

Λ ι '" ¹

> CII C CH

Br

(H ₂ CII Gl,

CH ₁ CW CII,

S ^ν "'S

% CH C CH - /

ν ' N ■■
i

I ₂ I ₄ SO,

N
C ', H ₁

CW C CH cn.,

ii / CH C CH

CMI ₅

i;

N '**'
, CH,), SO,

i ι

N '"- ■'

(CH,)., COOH

Through the discovery it is achieved that through the \ erwendum; the special combination of sensitizer dyes a photographic material is obtained which has a panchromatic, the green and the red Spcktralbereieh overdeckci: the sensitization of the highest red standard which has a sensitization maximum in the 1111 range from 625 to 665 nm.

(In a special embodiment of the original, a recording material is created. That is, at least one spectral sensitizer dye substance of the firm I. wherein the groups Z ₁ and Z _{2 are} a sulfur atom Phenyl group or methyl group, and at least one special serisibilizer dye of the general formula! II enih.il ;.

According to a further embodiment of the invention, a nucleus-substituted benzothiazole or Ben / oselena / oltrimcthincyanin used of the general formula II, in which the substituted alkyl group corresponding to residues R, or R ₃ of the ^F: Ormel II of an alkyl group. which contains a sulforest. an alk>! group that contains a carboxy radical. or which consists of an allyl group.

Through the above-described Ausgesialr.iiiiien Herds achieved superior results in terms of 'awareness raising'.

The sensitizers according to, ilkvn ^ ι; κ ν formulas I and 11 by conventional V can drive ei be made: for example, you konneu dyes corresponding to the general I> rm ■;. I.

4S according to the procedure of the l'SA.Patenischrin 2 50 ^; '"<> of the German patent specification 1072 765 and the i.tp.i nischcn patent application 6 ¹ MI 466 hergesuH; wci den and the compounds tier 1 <·, ik! I can correspondingly tier IiSA - Ι'.ιι-ίη ^ Ι-πΙ 2 503 776. of the German Palentschrift 92 ^l »i) ;; n to the Japanese patent application 6S-65 7 () 4 Iier 1 ...

The following is a method of manufacturing of the spectral sensitizer ·, (I B) as upische- Bei game given for a dye of the formula I.

1 g of 5-methyl-3-l; -sulfoprop \ l! -2-thiopropioM \ methylenbenzothia-olin and 1.5 g of methyl-p-toliu ■! sulfonate were heated to III) C for 2 hours! then cooled and washed with ether. The reaction product was then dissolved in 160 ml ^; Dissolved \ tha.io and added! .4g of anhyciro-5-carbr.meihow 3 - (; '- siilfopropyl) -2-methylbenzothiazoiu; .nih \ dnv.; i <and 2 ml of triethylamine and heated to reflux for 3 hours. After removal of tk: s I. övjhus by means of treatment of the residue, the crude crystals were first treated with ethyl ether and ai: then with a mixture of ethanol. Acetone obtained. 9CK) mg of pure crystals (Schmel /

L -.

2

Point 14 (1 Cl were removed by impregnation tinein demised from ethanol iiiul isopropanol receive.

The other sensitizers used in accordance with the invention bsiofie can according to, analogous procedures / u * the one described above.

Some physical constants of typical oil dyes. which are used in the context of the lituliing white and repeated by the general formula I. are in the table below specified. Of course, they are wet replaceable sensitizing dyes are not affected limited.

551.5

552

554

557 SW. 5

arhsioll Ni Sihim.-1 / piiMk (I I Ι-Λ 26? 1-1 « 140 IC 242 I-I) above M) O 1-1: I 75 I-E I <5

The procedure indicated according to the invention Spectral sensitivity is for (iclatine-silver-Ih.'logeniil-E. emulsions effective, but can also be used effectively to sensitize emulsions that contain hydrophilic colloids other than <: elaline, e.g. from collodion Agar, water-soluble cellulose derivatives. Polyvinyl alcohol, other hydrophilic synthetic or natural resins.

l'photographic. mixed silver halide emulsions. for example Silhei broinjodid and silver chlorobromoiodide are preferred in the context of de ' Inauguration used.

The spectral sensitizers to be used according to the invention are in water or a water-soluble organic solvent. for example methanol. Ethanol. Acetone. Melhy lcellosoive and the like., And then these solutions 4.s are added to the silver halide emulsion either separately or in the mixed state. The ratio of the spectral sensitizing dyes contained in the emulsion of the general formula! To that of the general formula! Can be within sometimes the range 20.1 to 1:10 can be varied according to the desired effects. The photographic emulsion according to the invention can also supersensitize or hypersensitize processes known to Bach. Furthermore, various additives can be used in the production of the photographic emulsions according to the invention Chemical sensitizers, stabilizers, toners, hard surface-active agents, anti-dilation agents, plasticizers, development ^{accelerators,} fern couplers and fluorescent brightening agents! : on suitable carriers, for example ice made of glass. Film bases made of cellulose derivatives or synthetic resin films. on photographic baryta papers or synthetic or semi-synthetic plastics similar to paper.

259 /

Examples 1 to Ψ

Three types of photographic silver halide emulsions were prepared by adding the spectral sensitizers to pholographic superbromide emulsions (Ag.l: / \ gUr - 7:93 mol), (II being the non-specific sensitizer of the general formula 1. (2) the applied sensitizer one of the general formula II and (3) the sensitizer used consisted of a combination of the dyes of the formulas I and II. Each photographic emulsion was coated on a cellulose triacetate film base and dried, and the photographic sensitive material obtained. The photographic sensitive material obtained was obtained exposed to light with an intensity of 64 Lu \ corresponding to a color temperature of 5400 K through a filter which only transmits light longer than 580 nm and then develops with the developer of the composition given in Table I.

Table I.

Methol 2 g

Sodium sulfh 100 g

Hydroquinone 5 g

Borax 2 g

Water to | |

The results are in Table 11 below shown.

Table I!

i, l
pn- ^: ι .11 Iv
slnff
No 4th ΜιΜίμο lies:
K | itiM | ien
StMlMlilll-,
! (1 ·>'MkI Vj! I 'MHtKlOIl M; i \ im; ilo
I niplmd
!! L · hku · 11 KkI-
cmpliiu
lkiikci 100 200 160 j I inuNiiinl
t: mini 6.1X 146 646 290 1X0 1 Λ 2 I.
I -I AgHr.! 640 66 640; IXO 640 140 2X0 "I. X the same 600 50 652 ι 100 640; 245 255 A. J - '° the same 640 652 i 125 662 i 140 195 2 4th X the same 646 j 226 62X; 150 A. 1-7 the same 630 646; 275 .1 H S. the same 656 E. χ ■ - 0.5 the same 628 4th B. X the same 650 .1 5 X the same 650 B. ■ 6 * 2; the same 662 5 F. : X i the same E. 1 1 _ ₍ ^ the same Λ D. 5 It) the same S. S. χ the same : 6 - 2 ^: the same ! χ the same I. ! X the same C. - 6-2 the same X C. : 6-2 the same ι) D. + S - 1 the same

In Table II, each value in the column shows »Roiempfmdlichkit ·. the value compared to the red sensitivity of the photographic emulsion which

409 639/317

6th

with the sensibilisato; E has been sensitized and mil Light through the red filter, this merely light one Wavelength above 5X0 to pass through, exposed would. The sensitivity of this emulsion was assumed to be 2ii 100. s

It is clear from Table II. That when used the silage dye I and II in combination the red sensitivity was markedly and strongly increased compared with the case in which the sensitizing dyes I and II used individually became.

To prove the technical superiority of the Comparative experiments using the sensitized silver halide emulsion of the present invention were carried out of the dyes indicated below.

10

The same conditions in terms of the preparation of the emulsion, the exposure and the the development iiiigcwenilel. as in the preceding IkispieL-n are described. The one with it The results obtained are shown in the following ■ column. In this, .S '/' i red sensitivity) the relative sensitivity assuming that the dye (11-1). used in a Amount of 8 ■ 10 ^ mol kg of emulsion, a sensitivity of 100 possesses, the .S'w I Wcißensenslehkeil) denotes a relative sensitivity, assuming that the sensitivity of an emulsion, which does not contain any dye. 100 is.

The spectrograms were obtained using a grating spectrograph with a tungsten light source of 2666K received.

Comparison dyes used (described in French patent I 497 142)

Cl

S. X (TI CH,
I. S. j: n ' C. i C. C (Tl N ^; (CH ₂ U SO, H N
I. Br Se, -. C ₂ \\ _s s, - ■ ·. S. CW C ₂ IL ----- ' \\
N ■ N CCH
Br C ₂ H ₅ C ₂ H ₅ s, -. ir. CH C ₂ H ₅ Ii C CH N ' 4SO, (CH ₂ I. ir. CW CH, C = CH

N N ''

C ₂ H ₅ (CH,), SO,

Dyes according to the invention

HOOC

CH ₁ OOC

S ^ " ^s S

-CH = CCH =; '

N N

I SO,

CA

(CH ₂ J ₃ SOjHN (CH ₂ H ₅ ).,

A A

-CH = C-CH = /

N
(CH ₂ I ₃ S N '■ - (CH,), SO, HN (C, H ₅ ),

- r C

S. CII CII ₁ S. C CII N Hi N (Ml (,

CH,

(Il C (Il

\, mu
I.! Rl · ..!
McilL'c I. (K i mli'ivi
in Μ. I .nbM
! ι Wed: ih: o Ml- i ill- IH
ill
III (Ml ₅ .ΊιΊ
mill
MnI .Sn 1
* - ι For this HiIvIIc N III .SY LnipliiHlhch
wedge iKcliiliv-
world 2 j (1-1 4th «Ll,) ₄ p I inplinilliih-
«.- ■» ΐΚι-Ι.ιΐιν-
uu r! ι; I. ί: I. X 100 }} 4th S 6 77 i LTNiK h Ni χ 4th 91 ■ Ii sy i H-I HI KX) 103 Ί 4 I) no 4th HI- 2 no S. 4th no 3 (a) X KH) I 4 106 X ' Ml- 96 31 93 no 4th 130 ■: - 4 lh ' • I 4 3) 6th 130 4th I. τ 120 4th 145 4th i35 4th j lo'l Il 6th KK) X iOO lh ') ■) 103 4th : ld ') 111) 4th 110 2 no 4th no S. χ no 90 4th 103 50 106 91) 4th no K) O X χ; no 150 X no 150 110 175 1 sheet IXO τ 90 90 M) 4th IIS 4th 120 2 120 ^4th ISO 145 5 X 62 6X 120 130 120 60 67 73 i '- X 6 150 127 ! 2O drawings

0.04 0 04 0.04 0.04 0.06 0.07 0.09 0.05 O.07 0.05 0.07

0.04 0.04 0.06 0.06 0.1) 6 0.06 0.06 0.06

0.07 (UiX 0. (IX 0.09 0.09

0.07

O.OX 0.06 0.06 O.OS 0.08 0.08

j ^ pL-ktl.'LM.I

! Fi μ. I.

Claims (1)

2 I 16 259 Patent claims: I. Phatagraphical recording material with a light-sensitive material applied to a layer support Silver halide emulsion layer, caused by a content of a sensitization alarm mixture is spectrally sensitized, which consists of at least one nucleus-substituted, ms-ethyl-substituted Benzthiazole and / or benzoselenazole trimethine cyanine of the formula