DE2145407A1 - Spectrally sensitized silver halide photographic emulsion - Google Patents

Description

PATENT LAWYERS

DR. E. WIEGAND DIPL-ING. W. NIEMANN 214540 /

DR. M. KÖHLER DIPL-ING. C. GERNHARDT

MÖNCHEN HAMBURG

TELEPHONE: 55547 «8000 MDN CH EN 15,

TELEGRAMS: KARPATENT NUSSBAUMSTRASSE 10

W. 40701/71 Ko / D ¹⁰ September 1971

Photo Film Co. Ltd. Ashigara-Karaigun, Kanagawa («£ pan)

Spectrally sensitized silver halide photographic emulsion

The invention is concerned and particularly relates to spectrally sensitized silver halide photographic emulsions superpanchromatically sensitized photographic Silver halide emulsions formed using the combination of at least two selected sensitizing dyes were obtained.

It is an object of the invention to provide photographic light-sensitive elements with high sensitivity, which _{extend from -100 in "to 700 m * a of} the wavelength range. In order to achieve this wide range of wavelengths for sensitizers, at least two sensitizer dyes are generally used in combination, and in this group it is customary for the combination to be used

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maximum achieved by at least two sensitizing dyes Sensitivity is lower than that obtained by using each dye alone. However, will a high spectral sensitivity superadditive "when applied obtained from more than two sensitizing dyes in a specific combination and this phenomenon is known as supersensitization.

It is an object of the invention to combine a group of sensitizing dyes which specifically give the supersensitizing effect and give high sensitivity in the wavelength range of 680 to 550 η .

In the accompanying drawing, FIGS. 1, 2 and 3 are graphical representations of spectrograms used for Serve to explain the invention.

Generally speaking, a dye has a spectral absorption, which sensitizes the emulsion over a long range of wavelengths, has numerous disadvantages compared to another dye with this spectral absorption, which has the emulsion in a short wavelength sensitized. For example, the disadvantages occur that the desensitization in terms of self-absorption of the light of the silver halide emulsion is more noticeable, there is a tendency to decrease the Effectiveness of sensitization occurs and there is also a tendency to fog formation.

It can therefore be assumed that, although the maximum absorption wavelength of the isolated molecule. Of the dye even belongs to the short wavelength, this dye has an absorption peak in the longer wavelength range when it is adsorbed on the indicated silver halide grains, particularly when the dye a J band in the case of adsorption on the silver halide grains in the emulsion that this is beneficial for

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the object of the invention is. From the point of view of J-banding effect, a strong selectivity for combining the sensitizing dyes is required. Of the Partstoff, the sensitivity peak in the range of the longest wavelength of a group of to be combined Has dyes must be most suitable for the formation of the J-band and in this pail the J-band must not be destroyed by the other combined dyes or other additives. With another dye a suitable formation function of the J-band is required, i.e. if the formation function is too remarkable is, there arises a tendency that a supersensitization function hardly occurs and also a uniformly high one spectral sensitivity distribution can hardly be obtained.

For the various reasons given above, it is generally believed that a derivative of a selective combination of a group with supersensitization is not possible based solely on similarities in the chemical structural formulas.

In the context of the invention it was found that the object of the invention and the improvements of the disadvantages the usual methods specified above can be achieved if a coordination of at least one carbocyanine dye it corresponding to the following general formula (I) and at least one sensitizing dye correspondingly of the following general formula (II) is contained in a silver halide emulsion:

(D

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• 2U5407

A is a lower alkyl group, "for example methyl-, ethyl- or n-propyl group,

Y ^ and Yp / which can be the same or different, each a sulfur atom or selenium atom, Z ₁ an atom grouping required to form a haphthol ring,

Z _{2 is} an atomic grouping necessary for the formation of a naphthol ring, a benzene ring, which can carry substituents, for example lower alkyl groups such as methyl or ethyl groups, halogen atoms such as chlorine atoms or bromine atoms, hydroxyl groups, alkoxy groups, alkoxycarbonyl groups or carboxyl groups

R ^ and Rp lower alkyl groups, for example methyl, Ethyl and n-propyl groups, an allyl group or a substituted alkyl group with a Sulforest, for example a sulfoethyl group, sulfopropyl group, γ-sulfobutyl group, or £ -SuIfοbutylgruppe, where at least one of the groups R ^ or Rp is a substituted alkyl group with a Sulforest is,

X ^ an acid anion and.

ρ the numbers 1 or 2, where ρ is the number 1, if a betaine structure is formed, mean «

(II)

Ap is a hydrogen atom or a lower alkyl group, Z ^ a necessary for the formation of a benzoselenasole ring

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Atom grouping,

Z. one to form a benzothiazole ring or benzoselenazole ring. required atom grouping, where the by. Z or Z. formed heterocyclic ring can be substituted or unsubstituted and, for example, the heterocyclic ring can be substituted by lower alkyl groups such as methyl or ethyl groups, halogen atoms such as chlorine atoms or bromine atoms, phenyl groups, alkoxycarbonyl groups, carboxyl groups, hydroxyl groups or alkoxy groups

R-z and R. lower alkyl groups, for example Methyl, ethyl or n-propyl groups, ß-hydroxyethyl, ß-carboxyethyl, γ-carboxypropyl, S-carboxybutyl, ß-sulfoethyl, γ-sulfopropyl, γ-sulfobutyl,. -Sulfobutyl-, 2- (3 ~ sulfopropoxy) ethyl, ß-acetoxyethyl, sulfatoethyl or allyl groups

Xp an acid anion, for example a chlorine ion, bromine ion, Iodine ion, p-toluenesulfonic acid ion or perchloric acid ion and

q the numbers 1 or 2, where in the case of formation of a Betaine structure with R, or R. the value of q is the number 1, mean. - ■■ · -

Combinations that contain at least one sensitizing dye of the general formula (III) and contain at least one sensitizing dye of the general formula (IV), are preferred according to the invention:

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denote the above-mentioned alkyl groups with a sulpho radical;

where R, - and

(IV)

before in R ₇ and R _Q the lower alkyl groups with up to 6 carbon atoms listed above, A, a methyl or ethyl group and Z 1, Z-, X ^ and q have the same meanings as in the general formula (II). Another preferred example of combinations which are suitable within the scope of the invention are combinations which contain the dye of the formula (IK) and at least one sensitizing dye of the general formula (V):

C ₂ H ₅

₂ H ₅

CH = C-CH =

(I-K)

Se 'I 5

'X-CH = C-CH =

< ^X 2 \ -X

(V)

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where IU., R., X «and q have the same meanings as" at of the general formula (II) ″.

The sensitizing dyes represented by the above general formula (I) have the following three characteristic features: The first characteristic feature thereof resides in the fact that at least a part in the two heterocyclic cyanine nuclei consists of a β-naphthothiazole nucleus or β-naphtholselenazole nucleus. The second characteristic resides in the fact that the sensitizing dye easily forms a J band and particularly its maximum sensitivity is in a wavelength range of 650 m "to 700 mn and that" if the second characteristic is satisfied, the heterocyclic ring is substituted or not can be substituted. The third characteristic lies in the fact that at least one R ^ or Rp group has a sulfor group, the betaine structure likely to be formed with this sulfor group, further assuming that the J-band is formed thereby.

Of course, the substituents are not limited to those specifically specified above, provided that the the necessary conditions listed above are met.

The characteristic feature of the sensitizing dyes corresponding to the general formula (II) lies in the fact that at least one heterocyclic ring represented by Z, or Ί ,. is formed from a benzoselenazole ring. In this case, compared with the case where the two cyanine nuclei are composed of benzothiazole nuclei, the supersensitizing function obtained by the combination use with the dyes represented by the general formula (I) is not only more remarkable but also a more uniform spectral distribution of sensitivity is obtained. In view of this, was

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especially the teaching of the Japanese patent publication 4,933 / £ 8 "remarkably improved.

Furthermore, when the present invention is combined with the teaching of Japanese Patent Publication 23320/69, this is advantageous for producing a photographic photosensitive element having a high and practically equal sensitivity in the range of 400 Wa ₁ to 700 myu wavelength.

That is, monomethine dyes such as 2,2'-quinocyanine dyes and pseudocyanine dyes, preferably of the general formula (VI), can be used for the photographic emulsion according to added to the invention:

CH

•
/ I. ι 6
* (VI) 1
^R 10

where Z, - the atomic grouping necessary to form a ring of the benzene series, Zg the atomic grouping necessary to form a ring of the quinoline series, a ring of the benzothiazole series or a ring of the benzoselenazole series, while Rg, R ₁₀ , X, and r are the same Meanings such as R ,, R., X ₂ and q. in the general formula (II).

For example, the dyes A or B mentioned below can be combined with the sensitizing dyes can be used according to the invention:

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C-CH = C

C-CH = C

• ir I

(CH ₂ ) ^ SO ₃

In general, it is preferred that the amount of the monomethine cyanine dye to be used is in the range of 1 10 ⁶ mol to 1 χ 10 ⁴ mol per one mol of silver halide.

In the following, suitable dyes are specified specifically within the scope of the invention, but it goes without saying that that the dyes are not limited to those given here.

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(IA)

- ίο -

CH ₅

CH ₃

₂₅ = c HC = C Η

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/ C-CH = C-CH = CJ

ag-. . μ;

OH

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(IG)

CO ¹ OCHs

(CH %) 3 ^s °

ar

-CH = C-CH = C

(HA)

) c-0 H = C-O H = CSl I

. (CiI ₂ ). ^ SO ₀

0CH3

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(nc) (HD)

- 13 -

CH ₃ ο 1 ■. ■ /

V-OH = C-OH = G ^

Γ .1

'C »H5

CH ₃

OH

(HE)

1 ic ■ 1 * / / ß

CH-C-C H-θ;

■. ^: ι

1-Ο.Λ 'C ^ H ₅

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Oil-

gV

M M

CiJ H M

CiJ M M

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(II D

CHß

C 1 OH-; O = OH - '- C

-C ₂ H

- C 5> Jl η

Comparative dye

Π C- ^ CH-C-CH = O

IU4,. ^

(D)

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The sensitizing dyes of general formula (I) and (II) know by known methods, for example according to the TJS-Patentsehrift 2,503,776 _t British Patent 742,112, German Patent 1,072,765, German Patent 1,163,671 andthe US - Patent 3,177,210 can be readily prepared by those skilled in the art.

The sensitizing dye used in the invention is in an aqueous solution or a water-soluble one organic solvents, for example methanol, ethanol, acetone, Methylcellojaolve or pyridine and dissolved mixed with the silver halide emulsion or added separately thereto.

On the other hand, the sensitizing dye can be dispersed or Wasseijgelöst regard and the dispersion or solution obtained can be added to the emulsion in an oil having a solubility of less than 10 fo. Ultrasonic filtration can be used to dissolve the sensitizing dye. The amount added and the order of addition of the sensitizing dye or the timing of preparing the emulsion to be added and the method of adding them can be appropriately changed according to the purpose. In general, it is preferred that the amount of the sensitizing dye represented by the general formula (I) or (II) used is within a range of 1 10 mol to 4 10 4 mol per one mol of the silver halide. In addition, it is preferred that the amount of the dye corresponding to the general formula (II) to be used with respect to the dye corresponding to the general formula (i) is within the range of 1:10 to 1Q4 as a molar ratio.

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The amount of monomethine dye to be added is in the range τοη 1O "" ² mol to 10 mol per mole of the dye of the general formula I.

Examples of silver halide emulsions to be used according to the invention are silver iodobromide, silver bromide, Silver chlorobromide, silver chloroiodobromide and the like which can be obtained by conventional methods and chemical sensitization methods can be performed in a conventional manner can be applied to these emulsions.

Furthermore, anti-fogging agents, stabilizers, chemical sensitizers, development accelerators, surfactants, film quantity reforming agents or photographic dyes and required fills Color couplers can be added to the silver halide emulsions.

The emulsion obtained is applied to a suitable support, for example films made from cellulose derivatives, polyethylene terephthalate films, PbI carbonate films, other plastic films, Glass plates, baryta paper, resin-coated paper or synthetic paper according to the purpose applied. . .

The following examples serve to further illustrate the invention and the objects achieved by the invention.

example 1

One kg of a silver chlorobromide emulsion (Br ~ "content 17 Μο1 ~ $), which is produced using a transfer posting process and chemically sensitized was heated to melt.

The sensitizing dyes represented by the general formula (i) or (II) were added to the emulsion in an amount as a dye-methanol solution with that given in Table I.

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Concentration added and stirred in sufficiently.

For the matching dyes (C). And (D) a Methanol solution of these dyes with a certain concentration added to the corresponding silver halide emulsion and stirred in sufficiently.

Maintaining the Geraischewurden obtained for 10 minutes after the addition of each solution at a temperature of 4-0 ⁰ C, then added to an anionic wetting and curing agent, and applied the mixture thereby obtained to a film and dried, so that a sample of the photosensitive member obtained became.

The photosensitive member obtained was cut into two pieces, and one of them was cut into two pieces with a wedge exposure through a yellow filter No. K-12 made by Fuji Photo-Film Co., Ltd. using a sensitometer with a light source of 540O ⁰ K, which was obtained by applying a DG conversion filter (Davis-Gibson) to a light source with a larbtemperatur of 2666 ° K. Another sample was subjected to exposure using a GR-2 type spectrograph (reflex type diffraction grating) from Narurai & Co.,

Using the following developer, these samples were developed for 4 minutes at a temperature of 20 ^° C. and further fixed and washed with water, the film strips being obtained.

Composition of the developer:

Metoi 2 g

anhydrous sodium sulfite 40 g
Hydroquinone 4 g

Sodium carbonate (monohydrate) 28 g
Potassium bromide. 1 g

Water to 11

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The developer thereby obtained was diluted with water to its two-fold amount and the obtained Solution used to develop the above strips.

It became the densities, the yellow filter sensitivities (Sy) and the fog values are determined and diflse values are given in tables (l) and (II) with the corresponding relative values. The numerical values of Fig. 1, and 3 are listed as remarks in Table (i).

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Table I.

Color i (IA) : I. Trains 1 160 • 160 - 0 Color • Trains - <■ maxi / 685 Sv No Loading material (IC) sat 80 (5 x 10 " ⁴ ) 80 (5xlO ~ ^4). 160 material- (HD). sat times 685 evil No. (ID) lot 160 160 yienge 80 (IxIO " ⁵ ) Sensation '' 685 (IB) (Molkon 320 320 (Molkon 160 opportunity 600 JKTiXIl "■ * (IA) (ic) centering) centering) 320 ' Waves- 640 (IA) (IB) (HEL 160 640 . 66 ■ V '680 66 0.13 1 80 (5XlO "" ⁴ ) 160 610 76 0.15 (ID) .... 160 80 (5 x 10 " ⁴ ) (ΠΑ) (IIE) 610 *. 91 0.23 • 320 160 645 120 0.13 320 80 (IxIO " ⁵ ) 675 132 0.13 (HA) 160 600 150 0.13 (HB) 320 675 100 0.15 160 160 67.5 125 0.13 2 • 80 (IxIO " ⁵ ) 600 132 0.14 (HB) 160. 600 160 0.15 320 645 66 0.15 '' ■ 160 670 79 0.14 3 680 85 0.15 (nc) 680 95 0.20 680. 100 0.13- " 80 (IxIO " ⁵ ) 595 100 0.13 (nc) 160 640 125 0.15 320 • 640 50 0.14 160 675 50 0.13 4th 675 32 0.13 (HD) 680 91 0.20 • 680 100 0.13. 80 (IxIO " ⁵ ) 640 91 0.13 160 655 125 0.13 320 655 91 Oj 14 160 6V5 HO 0.13 5 79 O ₁ IjS 63 0.15 63 0.13 80 0.14 • 159 0.15 0.15

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Table ί (continued

Tr. Color
material Trains
sat
lot
(Molkon
centering) Color
~ material Trains-
sat
lot
(Malkon
centering) maxi
times
Sensation
opportunity
waves
length
(m / u) Sy No
evil Loading
mer-
k-
gene 6th (IE) . 80 (5x10 "^)
160
520 (HI) 80 (5xlO ~ ⁴ )
160
520 670
675
675
640
640
640 55
45
50
91
100
100 . 0.12
0.12
0.15
0.15
0.15
0 _T 15 i) 7th (O 160 (5XlO * " ⁴ ) 600 "52 0.15 Li) 8th (IB)
(13) 160
160 (D)
(B)
(II I) 160 (5xlO ~ ⁴ )
160
160 600
670. *
675 100
112
125 0.15
0.15
0.15 Lü)
LV)
. ¹ I.
■ /

i) corresponding to curve 2 in FIG. 2

ii) corresponding to curve 1 in FIG. 1

iii) according to curve 3 in FIG. 2 iv) according to curve 5 in FIG. 3

v) corresponding to curve 4 in FIG. 3

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H β 'β * in in • O Φ O O r- VO Φ I ΉI ß-P Ο O' "* - CQ ß-P Φ O CO co ω Φ O CD I -P OM h in
Τ I -P I -P OM U O NW) H -P 1-I »Ο" H Φ Ν W) H-P W) -P β O β β Φ I W) -P flowed pi Φ © g φ I Ή M ß Φ'-ν Kj rag * - 'nt N CQg ^ - N O
τ— • Η Φ «Η, Cj φ W) .- < I «Η
.α «Η I «H O Ο MH P ₁ OH β N h o iQ Ή 00 CO CO CO B Ή mj .'Cd B CO-P U ο VD VD 'β PH 03 CO-P κΓ O Pq 03 I. I Ή A. O β-Ρ Φ O CO l «i I -ρ οΜ U Φ N W) H-P W) -P β O β P * Φ O) S φ O O Ν CQ gw tSJ I «Η , α «Μ f4 O ro-P fa co ΚΛ I. O τ— ■ v— '^^' O O VD VD ^^ H H I. O Τ "™
M. in O VD v— H

- 22 -

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Example 2

Instead of the emulsion used in Example 1, 1 kg of a silver odbromide emulsion (I content 4 mol $) applied -and the dyes added to this in the same way.

To the mixture obtained were 200 cm of a 5- ^ igen aqueous alkali solution with an incorporation type cyan coupler of the following structural formula is added and touched. The emulsion was then neutralized with citric acid to adjust the pH to 6.5 and then the emulsion is applied to a film in the same way as in Example 1 and dried:

Cyan coupler

As in Example 1, the photosensitive elements obtained were cut, exposed and developed for 7 minutes at a temperature of 20 ^° C. using the following color developing agent:

Composition of the color developing agent

Ιί, Ιί'-diethylamino-p-arainoaniline sulfate 2g Sodium sulfite. 2 g

Sodium carbonate (monohydrate) 50 g Hydroxylarain hydrochloride 1.5 g

Potassium bromide 1g

Water to 11

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The films developed in this way were subjected to a first fixation , bleaching, a second fixation and washing with water, and a strip of a cyan negative image was obtained in each case. The densities of the strips obtained were then determined using a red filter, the yellow filter sensitivities (Sy) and the fog values.

The values obtained are listed in Table (III).

Table III

Color Trains Color - 40 (HH) Trains ellen- sy fog material sat material sat length lot lot ^m / u) No. (MoI- (MoI- con- ⁴ V con- 680 80 0.15 (IA) Zen- 20 (5XiO ^-4 Ti Zen- 680 95 ^L 0.15 tration) 40 tration) 680 91 0.13 11 80 670 91 0.13 670 100 0.14 UIF) 670 95 0.15 20 (1x10 ~ ⁵ 673 250 0.14 (IA) 20th 40 670 91 0.13 (IG) 20 (5 10 " (HH) 80 670 96 0.13 40 40 670 100 0.14 12th 80 645 " 100: 0.13 545 112 0.14 545 100 0.13 2O (1x1O " ³ 550 125 0.14 (IG) 40 80 40

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Claims (10)

Yes tentansprttche A silver halide photographic emulsion characterized in that it is a combination of at least one Sensitizing dye of the general formula ; f> v. = G · - CH = C ^ JJ | ₂ ... _? . (I) where A * is a lower alkyl group, T ^ and Yp »^ ie are the same or different, a sulfur atom or a selenator * Z ^ an _{atom grouping necessary for the formation of a naphthol ring, s} Z" an atom grouping necessary for the formation of a Baphthol ring or a benzene ring ,, R ₁ and Rp ^e -E ^no lower alkyl group, where at least one of the radicals R ^ or R ^ a-us consists of an alkyl group substituted by a Sulforest, X .. "" «in acid anion and ρ di & numbers t or 2 _r where, if the dye betaine structure ^ "has _r ρ de» value has the value 1, mean, and at least one sensitizing dye according to the general formula M -CH = C- - CH = Ci; ORIGINAL INSPECTED 209812 / 1S87 wherein A ₂ is a hydrogen or a torn a- lower ^A lkylgrüj> pe,: Z, a zölringes to form a Benzoselena necessary Atomgruppi'erung, Z. a necessary for forming a benzothiazole ring ¹ or Benzoselenazolringes AtOragruppierung, R- and R, a lower alkyl group X ₂ " ^β ^ ^η acid anion and q [denote the number. 1 or 21, where, if the ear" material forms a betaine structure with R ^ or R ^, q; has the value 1 ". 2. Silver halide photographic emulsion ,, dadüreli characterized in that they are the combination of at least one Sensitizing dye according to the general formula in which R ₁ - and Rg are alkyl groups with a sulfate, and at least one sensitizing dye corresponds to the general formula R ₇ wherein R ₇ and Rg lower alkyl groups with up to 6 carbon atoms and Α. * a methyl or ethyl group and Z ^, Z. _r X ₂ "and q have the same meanings as in the general formula (II). 209812/1587 ORIGINAL INSPECTED _ 27 - · 3. Photographic silver halide emulsion, characterized in that it is a combination of a dye of the formula · (I - K) and at least one sensitizing dye of the general formula (V) CH = C _r CH ^ JJ J (I- K) CH ₃ CH = C-CH = q-1 (V) where R ~, R / »X ₂ ¹ ^ ^ have ^{the same} meanings as in
of the general formula (II). 4. Emulsion according to claim 1, 2 or 3, characterized in that the emulsion further comprises at least one 2,2'-quinocyanine dye ff or pseudocyanine dye as Contains monomethine dye. 5. Emulsion according to claim 4, characterized in that the monomethine dye from dyes accordingly the general formula / -Hv (VI) consists, in which Z ^ a for the formation! =? of a ring of the benzene series 209812/1587 2U5407 not \ 'that atom grouping, Zg an atomic grouping necessary for the formation of a ring of the quinoline series, the benzothiazoles ihe or the benzoselenazole series "and Rg, R ₁₀ , X, and r have the same meanings as the annuities R ,, R., X ~ and q in the general formula (II). 6. Emulsion according to claim 1 "to 5, characterized in that that the added amount of the sensitizing dye of the general formula (I) or (II) is within the -6 ' -A Range from 1x10 moles to 5 x 10 moles per one mole Silver halide. 7. Emulsion according to claim 6, characterized in that the added amount of the dye of the general Formula (il) with respect to the added amount of the dye of the general formula (i) within the range of 1:10 to 10: 4 as a molar ratio. 8. Emulsion according to claim 4 to 10, characterized in that the added amount of the monomethine dye in The range of 1 χ 10 ^-6 to 1 χ KT * moles per one mole of silver halide. 9. Emulsion according to claim 8, characterized in that the added amount of the monomethine dye in the The range is from 10 moles to 10 moles per one of the dye of the general formula (I). 10. Photographic light-sensitive material, thereby characterized in that there is an emulsion layer with a photographicη silver halide emulsion according to claims 1 to 9 contains. 209812/1587