DE2101071A1 - Light sensitive silver halide photographic emulsion - Google Patents

Description

Applicant: Konishiroku Photo Industry Co., Liä., Tokyo / Japan

Light sensitive silver halide photographic emulsion

The present invention "relates to a photosensitive, silver halide photographic emulsion containing a combination of sensitizing dyes. In particular concerns the present invention relates to an emulsion for the preparation of light-sensitive photographic recording materials of the so-called lith type, which have a hard tone and a result in a sharp raster image.

It is known that the photosensitive area inherent in a photosensitive silver halide emulsion is usually an extremely narrow one. Range (400 mp or less) of the ultraviolet or blue range . It is also known that the use of certain cyanine dyes is remarkably effective in the spectral sensitization of such silver halide emulsions. It is also known that when a combination of the aforementioned sensitizing dyes with certain other sensitizing dyes or organic compounds is added to a silver halide emulsion, the sensitivity obtained is greater than the sum of the sensitizing effects of the individual compounds. This effect is known as supersensitization. Many combinations of compounds are known to work with this in mind

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can be used.

When using the supersensitization method on a silver halide emulsion, in particular, a lith-type silver chloride-bromide emulsion, it is desirable that not only one Increase in the effect with regard to color sensitization occurs, but that the following requirements are also met.

1. The supersensitization process must not affect the properties the lith emulsion, which has an extremely high contrast supplies, adversely affect.

'dm Super awareness traverse en should help to improve the good dot quality of a raster image, without whose sharpness is adversely affected. 3 · The supersensitization should not produce color haze or haze after contrast development on the film.

Furthermore, it is desirable that in the case of a silver chloridbromide emu ion of the lith type, which is sensitive in the visible wavelength range, especially in the blue and green range, the supersensitization results in a high sensitivity in the blue range without affecting it per se inherent sensitivity becomes desensitized. By developing in a relatively short time from 'c. Sharp and good points should be obtained up to 3 minutes.

Most of the well known and mainly used to treat normal silver iodobromide emulsions for hegatives However, supersensitization processes cannot fully meet the above requirements when applied to silver chlorobromide emulsions which give a high contrast.

The present invention is based on the object light-sensitive, photographic silver halide emulsions

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deliver »who are supersensitized and the above .Requirements met.

The object of the present invention is also set based on photosensitive, photographic silver halide Finding winding materials are not called disadvantageous Interactions between the photographic additives present in this material enter »and at which stably maintain photographic properties even if the material is stored for a long time.

Haeh's extensive research has now been made surprisingly found that when using a combination of at least one compound of the general formula 1 not with at least one compound of the below mentioned formula II in a photographic silver halide emulsion only a remarkable effect in terms of color sensitization is achieved, but that also the above requirements to be fulfilled.

The subject of the present invention is a photosensitive, photographic silver uaiogenide emulsion, characterized in that is that they have at least one connection of the general ponael

(I) O = C-N

where P is (^ J ^ or [^ J and where H ₂ and f 'I

R ₂

Each represent an alkyl group, Q is a non-metallic atomic group forming a ssur · membered ring is' and R * ₁ or is a Aikjl "· -aryl" (Jruppe "

! 09830/1312

in combination with at least one compound of the general formula

CH - CH O

, C =

(ID

Ν '

where R, denotes an alkyl group, R, and Rg are each alkyl or aryl groups and Z ₁ and Z2 each represent hydrogen, a halogen atom or an alkyl, alkoxy or aryl group, in which 2

Formation of a benzene ring can be linked, contains.

and Z ₂ with each other

The compounds of the general formulas I and II are sensitizing dyes of the merocyanine type. When these sensitizing dyes according to the present invention are used in combination, the values for the unite spectral sensitivity maxima of the individual sensitization dyes to a common unified value for the maximum sensitivity that enables the best ortho sensitivity to obtain. This is due to the synergistic effect between the special ones according to the invention connections used. The sensitivity in the purple area and in the green area is remarkable in the case of the emulsion according to the invention elevated. The combination of the compounds according to the invention also has the characteristic effect that at the addition of which to a lith-type emulsion is possible, when using a lith developer containing hydroquinone as the main component together with an aldehyde get a sharp raster image with high contrast *

Typical examples of connections of the formulas I and II are listed below. The compounds which can be used according to the invention are not restricted to these examples. _ »Y_

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Examples of connections of different forms! I.

(A)

0-

R,

, L) - ο

C =

Ii

Mr.

(D (2) (3)

(B)

/ "> Tr. /""■, - Wi.- ■ ·» / ip

-GHpCOOH -CII ₂ CHpCK

-coon

R-

link Cc-O ■ - ¹ p 3 ^R l (9) . Ϊ-- - .. -O ₂ H ₅ -GpH ₅ . (ίο) -GH ₅ -O " ^G0 3 ^K (11) -CIU
3 -CH ₀ CH ₀ OH (12) - (CHp) ₅ SO ₅ K -CHpCIIpCOOH ■ (13) - -GH G- ^r OH -C ₂ II ₅ Q'O '- - -' '// \\' -CpH _r> H ¹ X) -CüpfJüü-r-CVir- - '' ',,! L- (16) —0! I.

rawjaytTT-r-T-

BATH ORIGINAL

! j C. -i. _rT S
I.
^R 2 ι link
Ur. (17) (18) (19) (20) (21)

Ο --- ο

- 17th

-CT

- ν * ι -

2 ^Γ >

. «- ^. _ ΓΛ
O ι
^ B ^ C = C
ι _ - 0
- IT
f 1 ^R 3 I.
R, I.
I? ^ C ₂ H ₅ link
No. -CH ₅ (22) -CIU (23) -CII,
3 (2'0 (25)

R-

25th

U - C - 7 * ~

10 9 8 3 0/131 2 BATH

(IO - 7 - -C ₀ TIf. \ O Ό
Ό 21Ü1U71 % -a- link
Mr. ■ O -CL ₅ (32)
I. (26) ^V 3 i ! i
^ C = CH-CII = C -K ^ -C ₀ ) Ic;
-CiIpCGCII (27)
(2Ö) link
No. GC -IZ '
I. (29) (30) -ο -CII-.
y - ° a ^{! I} 5 P,
X -CpH- 2 ' ^a 5 Typical examples of
of formula II are:
I. "(3D Binding , Kj -> J

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BAD DRfQINAL

ΙΐΟίΟΎΪ "]

(33)

.ο.

(CIL

c = Cn-CH = G-η.

0 = C- K ^

(35) CII ^ COCIT

G-CIi-CH-C

/ 1 '1

L Μ

(36)

(37)

^H 3 ^C. H ₇ C '

_ _T CH-CfXH

■ • - Γ'ττ (" ^Ί , ~, /" · - - τ ^τ / - Wi ι - OJJ-O i - ^

O = C-K

Cl

C ₀ H ι - - ^

. (cn ₂ ) ₂ so ₃ ii: - CPi = CK,

O = C-K

-9-

109830/1312 ΒΛ0 ORlGiNAL.

KILLS

CTT ₀ COOH

Cl ''

(r \ ' τ

-c—-:?

^ C = CII-

-N '

O = C-IT '

CH ₀ CH ₀ COOII

CH ₀ CHpOH ~ C - -S

CH ₀ CH ₀ COOH

0-C-N ''

-IP-

1Τ981QTi 3 If

BAD ORfGINM.

A. photographic recording photosensitive material that with an emulsion according to the present invention, which by adding the above-mentioned compounds supersens ibiiized has the excellent ones mentioned above Properties and shows ideal color sensitivity The combination of the compounds according to the invention imparts recorded properties not only to suitable recording materials from LittHPyp, but also light-sensitive photographic recording materials containing other silver chloride or silver chloride bromide emulsions contain *

The distribution of the wavelengths of the maximum sensitivity of the silver halide emulsions according to the present invention varies depending on the type and amount of the sensitizing dyes of the formulas I and IJ. The sensitizing dye β can be added in the form of a solution in a bit of water-miscible organic solvent, such as methylol Qtfariiianol. Alternatively, individual sensitizing dyes are added separately in the form of a solution in such an organic solvent. The addition of sensitizing dyes to the silver halide emulsion can be made at any stage during the preparation of the emulsion. However, it is generally preferred to carry out the addition after the second ripening. The amounts of the sensitizing dyes to be added vary depending on the kind of the silver halide emulsion used. As a rule, the total amount of the sensitizing dyes of the formulas I and JI is in the relatively wide range from about 1 μg to 200 mg per kg of the silver halide emulsion. In this case, the mixing ratio between the sensitizing dyes of the formula I and the sensitizing formula II is preferably as follows: 1 $ 10 and 10s1

% v, s α as weight.

The silver halide emulsions used by the invention unit are for example silver chlorid-, SilberchlcaridbroiBid- and

These emulsions can be used as usual

. -11-

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Sensitizers such as precious metal and sulfur sensitizers, or with polyalkylene oxide type compounds as the contrast remedial agents have been added. In addition, the emulsions can be visible over the entire length if desired The area has been visually sensitized by additional Incorporation of other sensitizing dyes, e.g. Carbocyanine dyes. Especially if you are sensitive to red what is desired is the use of thiacarboeyanine dyes advantageous. The emulsions can furthermore conventional photographic additives such as stabilizers, hardeners, coating auxiliaries, etc. contain.

The silver halide photographic emulsions described above which contain the individual compounds mentioned are in each case on a suitable carrier such as glass, cellulose triacetate, Polyester or paper applied and then dried, whereby light-sensitive photographic recording materials containing silver halide can be obtained according to the invention.

The invention is explained further on the basis of the following examples. These examples are not intended to limit the invention b e s Ehränken

example 1

A lith-type silver chlorobromide emulsion containing 2.0 mol # of silver bromide which had been treated with a gelatin coagulant was subjected to the second ripening process by the Golds ens ibi Ii sieruqs method and then divided into several portions. Each portion of this emulsion was mixed with methanolic solutions of the compounds listed in Table 1. Subsequently dieEmulsionen20 were min. Allowed to stand at about 40 ⁰ C, to stabilize the sensitivity. A suitable amount of polyalkylene oxide derivative was then added as a harder clay-providing agent, as well as a hardening agent and a coating aid.

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sensitive light-sensitive recording material of the Li th type to manufacture.

For comparison, a control sample was made in the same way but using "both sensitizing dyes e (a) and (b)." their formulas are shown below and which are disclosed in U.S. Patent Specification 2,977,229.

Control dyes:

C ₂ H ₅

These samples were each filtered through blue and green

Transmission maxima at 450 mji and 525 mu, respectively, were exposed at 125 lux (2.660 K) using a KS-VII model sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.). . Then 3 min at 2O ⁰ C was developed with a developer of the following composition:

Hot water Addition product of formaldehyde and sodium sulfite hydroquinone Sodium carbonate boric acid

500 ml

50 g 19 g ÖO g 10 g

-13-

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Potassium bromide water except for

2.2 g 1000 ml

The results obtained are summarized in Table 1. In this table, the relative sensitivity is a calculated value assuming that the Green sensitivity of the control sample with the dyes (a) and (b) is based on 100. The color haze is a density value obtained by using a complementary color filter was measured.

Tabel

Sample quantities of the assigned no. added compounds (mg / kg emulsion)

relative relative Äeaifärb Purple green density sensitivity sensitive (colourfulness lichfceit gehleier)

Control ( ^a ) dyes _(b) ^

(1) 50 mg

(34) 50 mg

(1) 30 mg + (34) 30 mg (9) 50 mg

(35) 50 mg

(9) 50 mg + (35) 50 mg

(19) 50 mg

(37) 50 mg

(19) 30 mg + (37) 30 mg

60 100 0.03 80 60 0.02 60 90 0.03 100 150 0.02 100 50 0.02 40 80 0.02 120 170 0.02 90 60 0.02 50 85 0.03 110 140 0.02

From Table 1 and the drawings it can be seen that the samples, containing a combination of compounds according to the present invention, better sensitization in the individual sensitivity ranges show as the samples which contain only one compound each, and that the samples according to of the invention exhibit greater sensitivity and less color haze than the control sample.

In the accompanying drawing, Fig. 1 is the spectral sensitivity curve a silver chlorobromide emulsion. Fig. 2 the

-14-

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-H-

Spectral sensitivity curve of sample No. 2 (dashed Line) and sample No. 3 (solid line); and Fig. 3 is the spectral sensitivity curve of sample 4 according to the invention;

Example 2

Example 1 was repeated with the modification that individual emulsion portions were each with the combinations specified in Table 2 compounds were added to prepare green-sensitive lith-type photographic recording materials. The serisitometric examination of the individual samples was carried out as described in Example 1 and the relative sensitivity was calculated. The contrast is expressed as the average gradient between the point where the density was 0.5 and the point where the density was 2.0 scam. The points were assessed in such a way that the sample in each case was in close contact with a contact screen brought, exposed and developed under the same conditions as in the case of the sensitometric examination. The obtained points were visually examined using a microscope. The assessment of the points is based on the grades 1 to 5, with those points being assessed with a grade of 5 that showed no interference and the highest sharpness. The grade 1 was given to those points which showed an extremely large number of interferences. The control dyes were the same as in Example 1.

-15-

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Sample no.

Amounts of added compounds (mg / kg emulsion)

Control (&) 30 mg + dyes (b) 30 mg

(4) 30mg + (32) 30mg

(Ό 30 mg + (35) 30 mg

(11) 30mg + (38) 30mg

(11) 30mg + (34) 30mg

(22) 30mg + (39) 30mg

- 15 - rel.
green
sensation
opportunity 210 1071 rel.
purple
sensation
opportunity 100 Con
touch Beur
division
the
Points 60 230 8.0 2-3 180 150 11 3 100 220 VJl 5 160 200 12th 4th 190 240 12th 4th 200 11 3

17 (22) 30mg + (4I) 30mg 170

190

13th

It can be seen from Table 2 that Samples Nos. 12 to 17 according to the present invention were compared with the control sample in every respect, i.e. sensitivity, contrast and point quality have better properties.

Example 3

A silver chlorobromide emulsion containing 20 mol% of silver bromide was subjected to the second ripening process and then divided into several portions, to which the combinations of dyes indicated in Table 3 were added to each one. The emulsions in the red area were then sensitized by adding the amounts given in Table 3 of a 1: 1 mixture of anhydro-3,3 «-X-sulfopropy 1-9-ethy1-4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide ( hereinafter referred to as "Red 1") and 3-T-sulfopropyl-9-ethyl-4,5-dibenzo-3 '>ü-sulfobutyl-5'-methylthiacarbocyanine sodium salt (hereinafter referred to as "Red 2 ⁿ ) After that, the same additives as in Example 1 were added to ^{J to} prepare panchromatic sensitized light-sensitive materials of the Liti type.

The sensitometric investigation of the samples produced in this way was carried out in such a way that the samples passed through blue and green filters, as used in Example 1, and a red -16-

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filter ι the light with a wavelength of more than 600 ΐημ passes through, exposed and then 3 min. At 20 ⁰ C with a D-11 developer from Eastman Kodak & Co. were developed. The results obtained are summarized in Table 3. In the table, the relative sensitivity is the calculated value assuming that the sensitivity of the sample containing only the red-sensitive dye Red 1 was taken as 100.

Tabel

Sample quantities of the added no. th connections
(mg / kg emulsion)

relative relative relative relative tive purple- green- red-sensation-sensation-sens- Ugliness ugliness

Control sample containing only the red sensitive dye (Red 1) 20 contains mg. 100

(5) 20 mg + (33) 20 mg + (Red 1) 20 mg + (Red 2) 20 mg 280

(14) 20 mg + (31) 20 mg + (Red 1) 20 mg +

(Red 2) 20 mg 220

(26) 20 mg + (38) 20 mg + (Red 1) 20 mg +

(Red 2) 20 mg 170

100 190 160 130

100

10b

110

100

0.08

0.08

0.09

0.08

From Table 3 it can be seen that even if the compounds according to the invention together with a red-sensitive Sensitizing dye used, the samples according to the invention have excellent photographic properties own.

Claims ;

Z.

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Claims (1)

Patent claims each represent an alkyl group, Q a non-metallic group Atomic group required to form a five-membered ring, and E- is an alkyl, Represents allyl or aryl G group, in combination with at least one compound of the general formula CH - CH = C O = C- wherein R ₄ denotes an alkyl group, R ₅ and Rg are each alkyl or aryl groups and Z ₁ and Z «each represent hydrogen, a halogen atom or an alkyl, alkoxy or aryl group, in which Z ₁ and Z ₂ are mutually below Formation of a benzene ring can be linked, contains. 2. Emulsion according to claim 1, characterized in that flie as compounds of the formula I compounds of the formula 109830/1312 - and or I.
CH,
p. contains 18- _C - 2101071 -19- Cl • I.
O = C - Sr
ι
CH, π. \ j O
- N "^
I.
CHpCH = GH ₀ , Cu I.
O = C - • t
CH, 0.A- "^ C = S
■ K ""
i
CHpCH ₂ SO ₃ K, (T
CH,
P. ... r S ^
^. Kt -0
ι.
I.
CH ₂ CH ₂ OH _t ■■ V / -
I.
O = C - S _x
I. (T
I. -.C- ^ TC = S
I. !
O = C - 109830/1312 5. Emulsion according to Claims 1 to 2, characterized in that that they are compounds of the formulas as compounds of the formula II C _O H- _C - - C = CH-CH = C-N ι
O = C- H CH ₂ CH ₂ COOH CH ₀ CT-I ₀ OH O ^ I ^{2 2} ^ C = CH-CH = C-H J O = C - N ^ and or he: CH ₀ COOH I ² C = CH-CH = C-N, !
j O = C - N- contains. 4. Emulsion according to Claims 1 to 3, characterized in that that the total amount of the compounds of the formula I and the compounds of the formula II in the range from 1 mg to 200 mg per kg of the emulsion is. 5. Emulsion according to Claims 1 to 4, characterized in that that the emulsion is of the lith type. 109830/1312 Blank page