DE2113443A1 - Photographic silver halide emulsion for direct positives - Google Patents

Description

PATENT ANWXLTE

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

DR. M. KÖHLER DIPL-ING. C. GERNHARDT 211344 3

^M0NCHEN HAMBURG

Monks 15, March 19, 1971

NUT SAUMSTRASSEIO

W. 4o 42o / 71 7 / RS

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

Silver halide photographic emulsion for direct positives

The invention relates to silicon overhalide photographic emulsions and in particular to a silver halide photographic emulsion for direct positives.

It is known that by incorporating a sensitizing dye s into a photographic silver halide emulsion, which has previously been obscured and directly a positive image through exposure and development can give the silver halide spectrally sensitive

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is bilized. It is also known that by the kind of sensitizing dye to be added and the The amount of sensitizing dye to be added to the emulsion and the contrast of the resulting image will vary will.

Although generally the incorporation of a sensitizing dye into the direct positive silver halide photographic emulsion increases its sensitivity, it often happens that the maximum density (-D ", c. _V ) decreases and the contrast lowers and that sufficient images cannot be obtained.

It has now been found that the halogen-substituted hydroxyphthalein dye according to the following general formula I an excellent dye for maintaining a certain maximum density and a certain contrast and to increase the sensitivity 13t.

The dye has the following general formula

(D

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211 3ΑΛ3

where X ₁ , X ₂ . Χ: * »Xi and Ir represent a halogen atom, M a hydrogen atom, an alkali metal (such as Na or K), NH. or an alkaline earth metal (such as 1/2 Ca), m, n, L and ρ represent 0 or 1, q is 0, 1, 2, 3 or 4 and X- ,, X ₂ , XZ, Xj and X ₁ - represent a hydrogen atom when m, n, L, ρ and q are 0.

On the other hand, when a sensitizing dye of a silver halide photographic emulsion for Direct positives incorporate their sensitivity grow, but it sometimes happens that a so-called "re-reversion" becomes larger and a sufficient degree of whiteness cannot be obtained. Under the expression "re-reversion" is the appearance understood that in Pig. 1 of the drawing is represented by the dashed line of the curve, after which after the decrease the density in the characteristic curve or blackening curve the density grows again.

The extent to which the "re-reversion" occurs depends on the manner of forming the silver halide photographic emulsions however, the occurrence of this phenomenon is particularly severe when using a silver halide photographic emulsion by the halogen-substituted hydroxyphthalein dye is sensitized according to the above general formula I, and accordingly, practical Application of the dye considered difficult.

It is an object of the invention to provide a highly sensitive silver halide photographic emulsion for direct positives, which can maintain the specified maximum density and high contrast, not is accompanied by the re-reversion and the low minimum density Has.

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The object according to the invention can be achieved by taking the following general formula Compound of a silver halide photographic emulsion shown in II for direct positives incorporated by the halogen-substituted hydroxyphthalein dye which is represented by General Formula I mentioned above.

The compound has the general formula II

HH-A-MH-

(II)

in which Y = CH- or = N-, R ₁

Ro »

U and R. a

Y-carbon atom, a hydroxyl group, an alkoxyl group, an aryloxyl group (such as a phenoxyl group, an o-toloxyl group, a p-sulfophenoxyl group or a meta-l-taphthoxyl group), a halogen atom (such as a chlorine atom or bromine atom), a heterocyclic nucleus (such as a methylthio group or a Ethylthio group), an arylthio group (such as a phenylthio group or a tolylthio group), an amino group, an alkylamino group or a substituted alkylamino group (such as a methylamino group, a dimethylamino group, a diethylamino group, a dodecylaniino group, a cyclohexylamino-hydroxy group, a -cyclohexylamino-hydroxy group hydroxyethylamino group or a beta-sulfoethylamino group), an arylamino group or a substituted arylamino group (such as an aniline group, an o-sulfoaniline group, an m-sulfoaniline group, a p-sulfoaniline group, an o-anisyl- · '1098A0 / 1 598

amino group, a m-anisylamino group, a p-anisylamino group, an o-toluidine group, an m-toluidine group, a p-toluidine group, an o-carboxyaniline group, an m-carboxyaniline group, a p-carboxyaniline group, a hydroxyaniline group, an ITaphthylamino group or a sulfonaphthylamino group), a heterocyclylamino group (such as a 2-benzothiazole amino group or a 2-pyridylamino group), an aryl group (such as a phenyl group) or a mercapto group and -A- the meaning of -A -, - or -Ap- as below indicated, has

-A ₁ -

CK = CH

SO3H

'SO3H

COIiE

CK = CH

SO ₃ H

-CH2 - CH2-

SOY-I

or -

-C = C

means, where M is a hydrogen atom or a cation represents that gives the compound water solubility, and

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-A ₂ -

V / Λ- J / Λ

means, where »if. A Ap is, at least one of the symbols R- ^{1, Rp, R} 3 and E, has a -SCUM-containing substituent in which M has the same meaning as given above.

Practical examples of the compounds represented by the general formula I are as follows:

Connection 1-1:

ι KaO

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Connection 1-2:

Connection 1-3:

Compound 1-4: ρ HO

Rv-

Connection 1-5:

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■ / -

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Connection 1-6:

Connection 1-7:

Connection "1-8:

Connection 1-9:

Connection I-lo:

109 840715

Connection I-11:

The above-mentioned dyes represented by the general formula I are commercially available Materials.

Practical examples of the compounds represented by the general formula II are shown below given:

Compound II-l:

OH

OH

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fr

Connection- jEI-2:

ll

Compound II-3:

OOH3

■ β »

Link. II-4:

MVA

Compound II-5:

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- building

Ιϊ-6:

• NH

H-

WK ^

Compound II-7:

/ f ⁷

Compound II-8:

^ J

Compound II-9:

. NH

/ V

Connection II-lo:

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^iH

"Connection 11-11:

Connection 11-12:

■ - OIL

α *

Connection 11-13:

¹ U j " ^R!] "

NH-

\ i

Connection 11-14:

NH-

Connection 11-15:

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211 3A43

Connection 11-16:

GQ

Connection ΓΓ-17:

st> aN *

Connection ^ 11-

Connection 11-19 ":

Connection II-2o:

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Compound II-21s

Compound 11-22.

Connection 11-23:

■ ^r hU

Connection 11-24:

10 9 8 4 0/1

The compounds represented by the general formula II and applied according to the invention are in Japanese Patent Publication Ur. Io 773/68 etc. described *

The dyes represented by the general formula I, which are used according to the invention, show no sensitizing effect in ordinary negative or positive photographic emulsions or have a poor spectral sensitizing effect as compared with cyanine sensitizing dyes or merocyanine sensitizing dyes. However, it was surprisingly found that the dyes an excellent sensitizing effect on photographic silver halide emulsions for direct positives to have.

The silver halide photographic emulsion for direct positives produced by the dye according to general Formula I is sensitized, is characterized in that the photographic emulsion has a high Sensitivity without reducing the maximum density (D) and contrast by adding the dye Has. However, since the silver halide photographic emulsion for direct positives produced by the dye of the general formula I is sensitized, has the disadvantage that the "re-reversion" is strong and the minimum density (D.) is high, such a photographic emulsion is for practical purposes are not used,

As a connection to reduce the formation of the "re-reversion" and also the minimum density is a Desensitizing compound, such as "pinakryptol-G-elb"

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known to be effective. In Yfena, however, a desensitizing compound such as pinacryptol yellow is incorporated into the silver halide photographic emulsion. For direct positives which is sensitized by the dye represented by the general formula I, the maximum density (D) hardly decreases, but such an attempt has the disadvantage connected that the reversal sensitivity together with the reduction in the formation of the "reversion" and the minimum density is reduced.

If'jedoch the compound of the general formula II is present together with the dye of the general formula I in the direct positive silver halide emulsion, are surprisingly obtained the advantages that the maximum density hardly decreases and that the formation of the "Re-reversion" and the minimum density decrease, while the reversal sensitivity does not decrease, but in some cases even enlarged.

• While the "pinacryptol yellow" etc. desensitizing properties compared to ordinary photographic Shows negative or positive emulsions has the compound of the general formula II almost no de.sensitization properties for such photographic emulsions and has no influence on it. It is therefore very surprising that when the compound of the general formula II used together with the dye of general formula I. becomes, the formation of the "re-reversion" and the ininj.-nale Density are decreased.

Ss is usually expedient to a photograph! - see silver halide emulsion the dye of the general formula I and the compound of the general formula II to add as a solution to each of them. As a solvent

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for the dye of the general formula I can use water, Serve methanol and ethanol. As a solvent for the compound of the general formula II, water, Methanol and ethanol are used, optionally using an alkali such as sodium hydroxide as the solvent can be added if necessary.

The effective amount of the dye according to the general formula I for addition to the photographic silver halide emulsion for direct positives is 1 to 200 mg, preferably 10 to 100 mg, per kg of the emulsion. The effective amount of the compound of general formula II is from 5 to 2ooo mg, preferably up Io looo mg per ₅ kg.der emulsion. The ratio of the compound of general formula I to the compound of general formula II is from 1/5 to 1/50, based on weight.

In a silver halide emulsion for use in the invention, such silver salts as silver chloride, Silver bromide, silver chlorobromide, silver chloroiodide and silver chloroiodine bromide can be used.

Emulsification and physical ripening of the silver halide photographic emulsion used in the invention used can be carried out in the manner conventionally used for ordinary photographic Emulsions is used, but a salt of a Group VIII metal of the Periodic Table, such as a Iridium salt or rhodium salt, of the silver halide emulsion during the formation of the precipitate or during the physical ripening can be added. The silver halide used according to the invention is used to the maximum Density obscured by exposure or by a chemical fogging agent. That for such purposes

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chemical fogging agents used are said to fog the silver halide with no ill effects on the silver halide emulsion, usually TMourea dioxide, tin (II) chloride, formaldehyde or hydrazine applied. After the obfuscation process is finished, the pH and p. -

Ag

Value regulated if necessary, if necessary.

• A solution of the dye of general formula I is first added to a silver halide emulsion, and then a solution of the compound of general formula II is added to the emulsion, after which it is stirred well will. The silver halide emulsion is coated on a support. The solution of the compound according to the general formula II can before the addition of the solution of the dye according to the general formula I can be added or a mixture of them can be added to the emulsion will. Further, these additives can be added to the silver halide emulsion during ripening after washing with water. Moreover, ordinary Additives such as a wetting agent or a hardening agent are added to the silver halide emulsion will.

As a support, a glass plate, a gelulose derivative film, a synthetic resin film, or a film can be considered Baryta-coated paper, a waterproof paper, a layered paper, etc.

The invention is explained in more detail below using an example.

Fig. 1 is a graph showing the characteristic Curve or blackening curve of a known emulsion shows.

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Fig. 2 is a graph showing a characteristic curve or density curve of an emulsion shows according to the invention.

example

A silver iodine bromide emulsion (containing 1.3 mol. 6 iodine and 21.3 jial. # Bromine) was obtained by formalin obscured and their pH and P. values became 5.6

Ag

and 6.7 are set. The dye represented by the general formula I was added to the emulsion, which was subsequently stirred well, and then the compound according to the general formula II was added and the mixture was sufficiently stirred. The silver halide emulsion was coated on a triacetyl cellulose film support upset. For comparison purposes, a disguised silver halide photographic emulsion of the same composition as the above to that however, only the dye according to the general formula I was added, applied to the same type of film support. After drying, each of the photosensitive films thus prepared was through a step wedge using exposed on a sensitometer and then developed in a developing solution of the following composition:

composition

Metoi 4 g

Hydroquinone Io g

anhydrous sodium sulfate 60 g

anhydrous I sodium carbonate 2.5 g

Water to make up to 1 liter.

The direct positive image obtained by the development was replaced by a fixing solution containing sodium thiosulfate

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- 2ο -

contained, fixed, washed with water and dried. After that, the optical density of the image was measured using measured by a desensitometer. The results are given in the table below:

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Connection I. Tabel Sensation (D) (D
^v max ' ^v m in ^ (mg / kg- opportunity No. Emulsion) Connection II white (mg / kg light Emulsion) (relative value) 23 0.21 I- - 6 (27.5) 100 22nd o.ic I - 6 («) 100 22nd o.io 1 I - 6 (") II - 1 (400) - 95 22nd 0.C- 2 I - 6 (») II - 1 (400) .98 _u 22nd 0.C5 3 I - 6 (· ')' II - 1 (800) 95 23 0.0Ξ 4th I -6 (") il - 2 (400) 110 22nd 0.07 VJl I- 6 (-) II r- 2 (800) 100 23- 0.07 6th I - 6 (") II - 4 (400) 115 .23 0.07 7th I - 6 (") II - 4 (800) 112 23 0.17 8th 1-9 (30.0) II - 8 (400) 100 23 0.07 9 • I - 9 (") II - 8 (800) 100 22nd 0.03 10 I - 9 (") - 103 '23. 0.0 = 11th I - 9 (") II - 3 (400), 124 22nd 0.07 12th I - 9 ( ⁿ ) II - 5 (400) 124 23 0.05 13th I - 9 (") II - 6 (400) - 148 22nd 0.10 14th I - 9 ( ^tr ) II - 7 (400) 105 22nd 0.12 15th I - 9 (") II - 8 (400) 100 23 0.07 16 I - 9 ( ^M ) II - 9 (400) 120 23 0.09 '17 I - 9 ( ^M ) II -10 (400) 112 23 0.07 18th I - 9 ( ^w ) II -11 (400) 100 22nd 0.07 19th I - 9 (") II -12 (400) 98 23 0.07 20th I - 9 (") II -13 (400) 105 25th 0.0 " 21 I - 9 (") II -14 (400) 128 "22 0.03 22nd I - 9 (") II -15 (400) 105 23 ■ 0.05 23 I - 9 (") II -16 (400) 40 23 0.15 24 ' 1-8 (45.0) II -17 (400) 100 23 0.C5 25th I - 8 (") Pinacryptol Yellow 124 ■ 22 0.10 26th I - 8 (") (100) 102 22nd 0.C3 27 I - 8 (") II -18 (800) 102 23 0.0Ξ 28 I - 8 (") II -19 (300) 12Ö 23 0.05 29 I - 8 (") II -20 (800) 98 22nd 0.12 30th I - 8 (") II -21 (800) 100 . 23 0.09 31 I - 8 ( ^M ) II -22 (800) 100 32 II -23 (800) 598 BATH ORIGINAL 33 .11 -24 (8Ö0) 1 098AO / 1

The blackening curves of a few samples in this Examples are in the graph of Pig. 2 reproduced, with curves 2, 3 and 4 denoting Test numbers 9, 15 and 25 correspond. As can be seen from these results, there was a reduction the sensitivity observed in the sample containing pinacryptol yellow (pinacryptol yellow was added to the silver halide emulsion in place of the compound of general formula II, and the results 3ind as experiment number 25 in the table or as curve 4 in Pig. 2 shown for comparison).

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Claims (10)

Claims 1. Photographer see silver halide emulsion for Direct positives, characterized in that they at least one of the dyes of the general formula 2M ⁺ (X ₂ ) _n (D in which X ₁ , X ₂ , X ^, X / and X ^ represent a halogen atom, m, n, L and ρ represent 0 or 1, q. 0, 1, 2, 3 or 4, where when m, n, L, ρ and q. 0, X- ,, Xp, X ,, X ^ and Xc represent a hydrogen atom and M a hydrogen atom, an alkali metal atom, HH. or means an alkaline earth metal, together with at least one of the compounds of the general formula Y ^ ^ n ν X (H) contains, in which Y = CH- or = N-, R ₁ , and R. a hydrogen atom, a hydroxyl group, 109840/159 Sine alkoxyl group, an aryloxyl group, a halogen atom, a heterocyclic nucleus, an alkylthio group, a heterocyclylthio group, an arylthio group, an amino group, an alkylamino group, a substituted alkylamino group, an arylamino group, a substituted arylamino group or - a arylamino group, a heterocyelylamino group A- ~ ^A i ~ or -Ap- represents, where - CH = CH - SO ₃ M SO ₃ M ^O 3 ^M -CONH- "\ --CH.dbd.CH--" ν-NHCO- '' SO ₃ M SO ₃ M -f V, or _ / ~ A _ _C « _c _f \) SO ₃ M SO ₃ M SO ₃ M SO ₃ M means, where M is a hydrogen atom or one of the compounds dung represents a cation imparting water solubility, and -v or 109840/1698 where AA is ₂ , at least one of the symbols E ₁ , R ₉ , E, and E, has a -SCUM-containing substituent, where M has the meaning given above. 2. A photographic silver halide emulsion according to claim 1, characterized in that X- ,, X ₂ , X ^ and X. of the general formula I denote a bromine or iodine atom and E ₁ , E ₂ , E and E in the general formula II represent an aryloxyl group, an arylthio group, an arylamino group or a substituted arylamino group. 3 · Silver halide photographic emulsion after Claim 1, characterized in that the dye of the general formula I is selected from one of the compounds 1-1 to 1-11 is selected. 4. A photographic silver halide emulsion according to claim 5, characterized in that the dye of the general formula I consists of the compound 1-6, the compound 1-9 or the compound 1-11. 5. A photographic silver halide emulsion according to claim 1, characterized in that the compound of the general formula II is selected from one of the compounds II-1 to II-24. 6. A photographic silver halide emulsion according to claim 5, characterized in that the compound of the formula II consists of the compound II-4 or the compound II-8. 7 »Photographic silver halide emulsion according to claim 1, characterized in that the amount of 109840/1 598 Dye according to the general formula I is 1 to 2oo mg / kg of the silver halide emulsion. 8. Photographic silver halide emulsion according to claim -1, characterized in that the amount of Compound according to the general formula II is 5 to 2,000 mg / kg of the silver halide emulsion. 9. The silver halide photographic emulsion of claim 1 wherein the ratio the compound of the general formula I to the compound of the general formula II for the addition to the Silver halide emulsion is 1/5 to 1/50 by weight. 10. Silver halide photographic material with a layer of the direct positive silver halide emulsion according to claim 1. 109840/1598