DE2140540A1 - Silver halide photographic emulsions - Google Patents

Description

The invention is concerned with photographic SiI-berhalide emulsions, in particular improved SiI berhalide emulsions, containing a J-band sensitizing type coloring material. In particular, the invention relates to improved Silver halide emulsions which are a J-band sensitizing type coloring material used for green sensitization suitable is included.

As known from F. M. Earner Cyanine Dyes and Related Compounds, page 710, 1964, publisher Interscience, is known the sensitizationamaximura through sensitizing dye materials for silver halide emulsions (M-band sensitization maximum due to molecular absorption) near the absorption maximum by (free) coloring material in the aqueous Solution, however, slightly towards the longer wavelength side. Certain sensitizing coloring materials have sharp sensitization bands on the side of the longitudinal

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reii wavelength (25 to 50 mm) than the wavelength corresponding the M-band sensitization maximum. This is known as J-band sensitization.

In general, the coloring photographic sensitizing materials are divided into two classes, there is one class of coloring materials which make effective use of M-band sensitization in silver halide emulsions makes, and the other class consists of coloring materials that make effective use of the J-band awareness makes. With the coloring materials it is the latter class that the present invention is concerned with.

There are numerous staining materials that can cause J-band sensitization demonstrate. This EaIl describes all sensitizing staining materials that require J-band sensitization show, referred to as J-band sensitization type coloring materials for the sake of convenience, since there are it is very awkward to designate the individual chemical structures.

It is known that the intensity of J-band sensitization of a coloring material is determined by the chemical structure of the coloring material, the properties of the emulsion, for example Composition of silver halide, crystal system of silver halide, concentration of silver ions in the emulsion and the pH of the emulsion influenced. It also increases the intensity of the J-band awareness by precipitating agents, stabilizers, coating auxiliaries or a coupler present in the emulsion influenced. In many cases, other than the J-band 3-type coloring materials to the emulsion have sensitization added compounds have an influence on the J-band sensitization.

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The invention is concerned with relatively beard tinted photosensitive materials that bite relatively high sensitive materials and not soft-toned photosensitive ones Materials. These photosensitive materials include photosensitive materials for reproduction, such as sensitive materials for black and white printing, for example black and white printing papers, sensitive materials for color printing, for example Color printing papers, color sensitive films, photosensitive materials for typography,, hard tinted, photosensitive Materials for television and the like.

It is known that silver halide emulsions are used in a green-sensitive layer and a red-sensitive layer Layer of multilayer material for color photography spectrally sensitized. Furthermore it is

that

Known, multi-layer color materials, especially multi-layer sensitive materials for color printing, especially color positive films, are favored with regard to the following arrangement of the layers and the properties of the layers to achieve excellent sharpness, namely a blue-sensitive layer is closest to the support, the green-sensitive and red-sensitive layers have substantially lower photosensitivities than the blue-sensitive layer and each photosensitive silver halide layer contains a color coupler which forms a color image complementary to that of the multilayer photosensitive material. It is dai ^ to indicate that the sensitivity to blue light of the green light-sensitive layer and the red light sensitive layer necessarily considerably lower than the blue light sensitivity of the blue light-sensitive layer are _r wherein the blue light sensitivity of the green ^Ί iehtempfindlichen layer in the order of 1/10

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that of the blue light-sensitive layer in conventional color printing papers or color positive films.

Furthermore, the reproduction of hard-toned powders with little fog and staining is required for light-sensitive materials for color printing. This requirement does not favor an AgBrI emulsion and AgCl emulsion as a silver halide emulsion for the green light-sensitive layer because of the disadvantages that the progress of development in the AgBrI emulsion is slower than in the AgCl emulsion or the AgClBr emulsion, see above that soft-toned images result and the water washing step cannot be omitted due to the slow progress of chemical digestion or second digestion without water washing prior to chemical digestion. On the other hand, the AgCl emulsion causes the development to proceed excessively rapidly, so that a mist is formed far more easily than that of AgClPr-Pr ¹ UIfJiOnBn. Therefore AgClBr-J5 emulsions are more favorable for others

a sensitive material to print.

the

On the other hand, spectral sensitization of those who are sensitive to green light Layer of the multilayer material is well known and gives a green selective sensitization when using J-band awareness.

An improvement in color separation and safety in low light favors J-band sensitization green light sensitive layer of a sensitive I ^ terialR for color printing. The J-band sensitization depends on the J-band training strength and the absorption power Silver halide of the sensitizing dyes. Beyond that J-band sensitization depends to a large extent on SNNP the chemical structure of the dye used and the chemical composition of the silver halide in the silver halide emulsion away.

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BAD ORiQtNAL

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The remaining discoloration is subject to sharp standards. Spotting and fog due to the coloring material used in the spectral sensitization for sensitive Create materials for color printing as well as for sensitive materials for black and white printing.

One object of the invention is for those sensitive to green light Emulsions which cause practically no discoloration due to sensitizing dyes and these are suitable for relatively hard-tinted photosensitive materials and contain J-band sensitizing type dyes.

Another object of the invention is photosensitive Materials that contain a layer of a green light sensitive emulsion, which by such J-band sensitizing type dyes sensitized are.

^T ./ ^r ic, AgClBr emulsions are preferable in terms of the progress of development, fog and tint for hard-tinted photosensitive materials, especially for photosensitive materials for printing, but the AgCIBr emulsions have the disadvantage that they hardly allow J-band sensitization by dyes of the J-band sensitizing type. Various attempts have been made to remedy this disadvantage. For example, it is described in Photo Sci. Ing. 13 (1), 13-17 that the addition of KI or KBr to an AgClBr emulsion increases the J-band sensitization Λ / οη streptocyanin. However, the increase in the J-band sensitization of such an emulsion due to the addition of KI or KBr is at the same time of a softer shade and a tendency to fog accompanied.

The J-band sensitization depends on the chemical structure of the dye used and the composition

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of the silver halide in the emulsion used, as follows from the examples. For example, if the sensitization of an AgClBr emulsion by a, Oxocarbocyanine dye represented by the following general formula

= CH - C = CH

is considered, the dye has two phenyl groups as substituents G and G ¹ and shows strong J-Eand sensitization.

A dye *, however, in which at least one of the radicals G or G ¹ consists of a chlorine atom, shows no T-band sensitization and only gives a very high level if it is added in an extremely large amount scnwaclie J-band awareness. Furthermore, the J-band sensitization is usually weakened in the presence of a color coupler to such a dye in which at least one of G or G ¹ consists of a chlorine atom, and an extremely serious drop in sensitivity due to the breakdown of the J-band achieved by the presence of the color coupler. On the other hand, a dye in which both E.este G and G ^! Phenyl groups are strong J-band sensitization when added in large amounts and it shows high green sensitivity in the presence of a color coupler because the J-band does not break down. However, this dye causes a large amount of residual discoloration, so that it is necessary to increase the J-Pand sensitization by adding a small amount of this dye. On the other hand, causes a dye in which at least one of the radicals G and G 'from a chlorine

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atom, a faint remaining discoloration, itself if it is added in large quantities and \ causes little leverage. Also these dyes with at least one Chlorine atom need an increase in J-band sensitization.

I within the scope of the invention were for J-band sensitization suitable emulsions are investigated, whereby the properties of the silver bromochloride emulsions are retained, so that the silver bromochloride emulsion is tinted hard and a slight mist formation is achieved and v / was found that a silver iodobromachloride emulsion is sufficient strong J-band sensitization by a dye of the J-band sensitizer type which has practically no staining and gives poor J-band sensitization when used in silver bromochloride emulsions will.

In the production of the AgClBrI-Ernulüionen, which in the To be used within the scope of the invention, the point in time of the addition of the I ~ ions at the stage of production the silver halide emulsions have a significant influence. The addition of the I ~ ions must necessarily before or during the formation of the precipitate and it is particularly advantageous during the formation of the precipitation carried out.

If the I "" ions are added to the emulsion after the complete Formation of the precipitate are added, for example toi * emulsion at the time of chemical digestion, to the emulsion after the end of the chemical digestion or bu the with sensitizing dyes, plastic hardening materials, Transfer aids and the like offset linulsion ready to be coated the J-Band sensitization by the Parbs boffe of the J-Pand sensitizer type unstable. The fact that the effect

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of the I ~ "ions differ depending on the The time of their addition cannot be determined due to the composition of the silver halide used foresee or predict.

The AgI content of the halide components of the AgClBrI used in the context of the invention is considerable 'Meaning. AgI is effective in an amount in the range from 0.1 to 5 mol $, particularly in the range from 0.1 to 2.5 Mo1- $. When the amount of AgI is less than Is 0.1 Mo1- $, the J-band sensitization is through the J-band sensitizing type dyes of the same Order of magnitude than with AgClBr emulsions and it shows no improvement. Palis, on the other hand, the AgI content is greater than 5 mol #, an increase in J-band sensitization occurs, however, along with little progress in development and softening of the clay so that the use of the emulsion is practically impossible.

The content of AgBr among the halide components is that for hard-tinted photosensitive materials customary in the range from 15 to 95 mol #, preferably im Range from 30 to 90 mo1- $. The grain size of the silver halides in the AgClBrI emulsions to be used according to the invention is limited only to the extent that it is in the range of the grain size customary for conventional photographic emulsions lies. An average grain size of less than 0.6 microns is particularly effective for hard-toned photosensitive ones Materials.

The grains of the Silbox ¹ halide used according to the invention can be of regular size or of irregular shape. According to the invention, however, a particularly beneficial effect when using Silborha halide grains is more regular. Size or shape. Achieved. Emulsions,

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which are not monodispersed can according to the invention can be applied. However, the effects according to the invention are better when monodispersed emulsions are used.

If the AgClBrl emulsions used in the present invention are decomposed with dyes of the J-band sensitization type and are spectrally sensitized, a very effective J-band sensitization can be achieved. This is due to the fact that in the case of an AgClBrl emulsion, as compared with the case of an AgClBr emulsion, the adsorption strength of the J-band sensitizing type dyes for the silver halide is increased and causes a large increase in the amount of adsorption, including Fig. 1 is referenced. In Fig. 1 the curve represents the adsorption isotherm of the dye 1 for an emulsion used according to the invention and the curve B represents the adsorption isotherm of the dye 1 in an AgClBr emulsion for comparison, in each case at a temperature of 45 ⁰ Cj.

The investigations with. an electron microscope revealed that the above two emulsions were almost the same Have surface areas of the silver halide.

Since the amount of the J-band sensitizing type dye added is a small amount per mole of the silver halide achieves a J-band sensitization, after the treatment of the sensitive materials, which are made up of emulsions with a content of J-band sensitizing type dyes are decreased. Because according to the invention, a strong J-band sensitization if we-i, it is possible to use green sensitizing emulsions for use in color printing materials, v / with these emulsions at most a very small reduction in sensitivity in the presence of a dye

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coupler show.

This is believed to be due to the fact that the release of the J-band sensitizing type dyes by the color coupler 'by the increased adsorption of the dyes of the J-band sensitizing type in the AgClBrI emulsion in the. Compared to an AgClBr emulsion is prevented or prevented.

The blue sensitivity of the AgClBrI emulsion according to of the invention for use in multilayer materials for color printing is sufficiently low compared to the blue sensitivity the layer sensitive to blue light. AgBrI's own photosensitive region has absorption spectra of longer wavelength than AgClBr, so that the blue sensitivity of the lower blue sensitive Layer decreases. However, the AgClBrI emulsion according to the invention has the advantage that if the molar percentage of AgI is low, the blue sensitivity of the blue-sensitive layer practically does not decrease.

To improve the physical properties of gelatin emulsion films, the use of additives, for example dispersed substances of vinyl polymers with an anionic surfactant is described in British Patent 1,186,699. The dispersed Substances of this type usually prevent J-band sensitization. On the other hand, there is J-band awareness the AgClBrl emulsion according to the invention by such dispersed substances hardly influenced and there is no perceptible hindrance.

Compounds used as flocculants are disclosed in, for example, Japanese Patent Publication 27470/65, U.S. Patent 2,469,341, and U.K. U.S. Patent 1,135,622. During the flocculation

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usually prevent J-band sensitization, the J-band sensitization of AgCIBr! emulsions, which according to the invention are J-band sensitizing type dyes contained, hardly influenced by such flocculants and there is no perceptible hindrance.

Used as anti-fogging agents or stabilizers compounds used, such as benzotriazole, ITitrobenzimidazole, 5-l-nitroimidazole, mercaptans, 5-methyl-7-hydroxy-1,3,4-triazaindolizine and similar compounds usually act to prevent J-band sensitization.

However, the J-band sensitization of AgClBrI emulsions, the J-band sensitizing type dyes contained according to the invention are hardly hindered by these compounds.

Azo dyes used in the silver dye bleaching process are in Japanese Patent Publications 10 280/61, 9 587/64 and 25 768/64.

Although these azo dyes usually have J-band sensitization prevent, they hardly interfere with the J-band sensitization of the AgClBrl emulsions, which according to the Invention J-band sensitizing type dyes.

Regarding the production of AgClBrl emulsions according to the invention, the omission of a water washing step prior to chemical digestion allows a more sufficient one Progress of chemical digestion compared to an AgBrl emulsion.

Any of the dyes showing J-band sensitization can be used effectively in the invention will. However, J-band sensitizing type dyes particularly useful for green sensitization are used listed below.

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In particular, the compounds of the general formeini, II, III, IV, V, VI or VII are particularly effective:

1 /"

In the above formula, R denotes a hydrogen atom or a lower alkyl group, for example a methyl group, ethyl group, each radical T ₁ and Y, a hydrogen atom, a lower alkyl group, a halogen atom, for example a chlorine atom or bromine atom, a hydroxyl group, an alkoxyl group, for example a methoxyl group, ethoxyl group, an amino group, for example, an amino group, methylamino group, an acylanide group, for example an acetamide group, an acyloxy group, for example an acetoxyl group, a carbalkoxyl group, for example a carbethoxy group or an alkoxycarbonylamino group, for example an ethoxycarbonylamino group.

Each radical Yp and Y ₁ - denotes a hydrogen atom, a lower alkyl group, a halogen atom, for example a chlorine atom, bromine atom, fluorine atom, a hydroxyl group, an alkoxy group, for example a methoxy group, ethoxy group, an amino group, for example an amino group, methylamino group, an acylamide group, for example an acetamide group, an acyloxy group, for example an acetoxy group, a carbalkoxyl group, for example a carbethoxyl group, an alkoxylcarbonylamino group, for example an ethoxyoarbonylamino group or

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OBiGINAL INSPECTED

2H-0540

a 'Pheny! group.

The remainders Y ₄ and J _n or Y. and Y_ can be a 12 45

Be methine chain such that Y «. and Yp or Y. and Yj- with each other to form a benzene ring including a ring with a substituted nucleus can be. The radicals Y and Yg mean a hydrogen atom or a methine chain such that Y, and Yp or Yg and Y, inclusive of each other to form a benzene ring of a benzene ring can be condensed with a substituted nucleus, with the exception of 2 cases, where in a pail the pairs Y, and Yo as well as Y «and Y .. at the same time Form benzene rings and in the other side the pairs Yg and Y, as well as Y ^ and Y. simultaneously form benzene rings.

Each radical R ^ and Rp denotes an alkyl group, for example a methyl group, xthyl group., N-propyl group, hydroxyalkyl group, for example a 2-hydroxy ethy group, 4-hydroxybutyl group, an acetoxyalkyl group, for example a 2-acetoxyethy group, 3- Acetoxypropyl group, an alkoxyalkyl group, for example a 2-methoxyethyl group, 4-butoxybutyl group, an alkyl group with a carboxyl group, for example a 2- carboxyethyl group, 3-carboxypropyl group, 2- (2-carboxyethoxy) ethyl group, an alkyl group with a sulfo group , for example a 2-sulfoabhyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfopropyl group, 2-hydroxyl-1-sulfopropyl group, 2- (3-sulfopropyl) -ethy group, 2-acetoxy-1-sulfopropyl group, 3 -Hethoxy-2- (3-sulfopropoxy) -propyl group, 2- [2.- (3-sulfopropoxy) -ethoxy-7ethyl group, 2-hydroxy-3- (3'-sulfopropoxy) propyl group, benzyl group, phenylethyl group, a p .Sulfobonzylgruppe, a p-Carboxybenzylgruppe, a p-Sulfophenäthylgrupp e or an allyl group, where at least one of the radicals R ₁ or Rp is an alkyl group with an arboxy group or an alkyl group with a sulfo group.

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^, ,,. "-., BAD ORIGINAL

X denotes an anion, for example a chloride, bromide, iodide, thiocyanate, sulfonate, perchlorate, p-toluenesulfonate, Methyl sulfonate and ethyl sulfonate and η denotes the numbers 1 or 2. ■

CH-CH-

In the above formula, Z represents a group

^^ R
O or C ^ 4 »where the radicals R- and R _{R are} an alkyl group,

represent, for example, a methyl group or ethyl group, R 1 denotes a lower alkyl group or an allyl group, Y ₇ denotes a hydrogen atom or halogen atom, for example chlorine atom, bromine atom or fluorine atom, To denotes a hydrogen atom, a halogen atom, for example a chlorine atom, bromine atom, fluorine atom, an alkoxy! group, such as a methoxyl group, ethoxyl group, amino group, for example an amino group, methylamino group, an acylamide group, beispielsv / else an acetamide group, an acyloxyl group, beispielsv / ice acetoxyl group, or a Allcoxycarbonylaminogruppe, for example a Äthoxycarbonylaminogruppe, Yq represents a Vi ^r hydrogen atom, a lower alkyl group, a halogen atom, a hydroxyl group or an alkoxy group and Yq means a water first off atom, a lower alkyl group, a halogen atom, an alkoxy group, a phenyl group, for example a phenyl group, ρ sulfophenyl group, a carboxyl group, an alkox yoarbonyl group, a cyano group or a trifluoromethyl group

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and R _{11 represents} a hydrogen atom or a methine chain which can form a benzene ring _{upon condensation with Y 1 Q.}

The radicals Yq and Y ₁₀ can be a methine chain which can form a benzene ring including a benzene ring with a substituted nucleus on condensation with one another. It should be noted that the case where both the pair of Yg and Y ₁₀ and the pair of Y ₁ Q and Y ₁₁ each form benzene rings at the same time is excluded.

R ₁ , Rp, X and η have the same meanings as in formula I.

In the above formula, the radicals R are

and Rf- is an alkyl group, for example a methyl group, ethyl group, propyl group, butyl group and the radicals Y ₁ P and Y «,. a hydrogen atom or a halogen atom. The radicals Y .., and Y ₁ ^ mean an hydrogen atom, a halogen atom, an alkoxy group, for example methoxyl group, ethoxy group, butoxy group, an amino group, for example an amino group, methylamino group, dimethy1-ainino group, a Acylamide group, e.g. an acetamide group, an acyloxyl group e.g.

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methyl group, an alkylsulfonyl group, for example a methylsulfonyl group, a sulfamyl group, a Alkylaminosulfonyl group, "for example an ethylaminosulfonyl group, Diethylaminosulfony! Group, a Morpholine »sulfonyl group or a piperidinosulfonyl group.

The radicals R ₁ , Rp, X and η have the same meanings as in formula I.

In the above formula, R denotes a hydrogen atom or a lower alkyl group and Yg denotes a hydrogen atom, a halogen atom such as a chlorine atom or a lower alkyl group and Y ₇ denotes a hydrogen atom, a halogen atom such as a chlorine atom, an alkyl group such as a methyl group, an ethyl group, Propyl group, an alkoxy group or phenyl group. I ₁ Q denotes a hydrogen atom or a methine chain which can form a bensol ring including a benaol ring with a substituted nucleus on condensation with Y ₁ 7 and the radicals Y ₁ Q and Y ₂₀ denote a hydrogen atom, a halogen atom, a lower alkyl group or an alkoxy group .

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R., R ₂ , X and η had the same meanings as in formula I-

In the above formula, Yp _{1 represents} a hydrogen atom, a hydroxyl group, a lower alkyl group, a halogen atom such as a chlorine atom or an alkoxyl group, and Y _{22 represents} a hydrogen atom or a lower alkyl group and Yp represents a hydrogen atom, a lower alkyl group, an alkoxyl group , a hydroxyl group or an i-henyl group.

The radicals R., R ₂ , X and η have the same meanings as in formula I.

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In the above formula, the radicals Yp ^ and Yp ₁ - denote a hydrogen atom, a lower alkyl group, an alkoxyl group or a halogen atom, "for example chlorine atom, bromine atom.

R ₁ , R2, X and η have the same meanings as in formula I.

The dyes corresponding to the general formulas I and III can easily be prepared in accordance with the French U.S. Patent 1,108,788; and U.S. Patent Nos. 2,503,776, 2,912,329, and 3,397,060 produce.

Dyes other than those specified in these patents can also be prepared by similar processes.

The dyes corresponding to the general formula II can easily be prepared in accordance with US Pat. No. 3,364 and Japanese Patent Publication 14030/69. Those skilled in the art can easily find dyes according to the general formula IY according to Japanese patent publication 16169/68 and dyes corresponding to the general formula V according to the German Offenlegungsschrift 1 936 262 and dyes not specified there can be prepared by methods similar to those in these references getting produced.

The following are examples of dyes according to FIG Invention given, although these examples do not cover the invention limit.

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- * .-. A * _t - jr-tS *

2H-0540

Dye 1

Cl

-OH = C-CH

Dye 2

H ₃ CO

OCHr

Dye 3

CH ₃

-OH = O-CH = / j

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Dye 4

2HÖ540

- 20 -

Dye 5

"H ₃ O

O2H5

C H = CC H =

CH ₃

(CH-) ASO ₅ H. π (CoII ₅ ) 3

Dye 6

-CH = C HC H =

C0H5 ··. . ·

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JIß CIIg CKCH ₃

8Ο3

ORIGtNAL INSPECTED

Dye 7

CH = CH-CH

(CH ₂ ) _ö S0 ₃ H · M (C ₂ E ₅ ), 3

dye 5 '

Dye 8

• v. C.

CH «OH ~

OHgCHgSO ₃ ST

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OWOiNAt INSPECTED

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Dye 9
H ₃ C

K ₃ C

= ÖH-OH = CH

Dye 10

= 0 H - C H = CH-

Dye 11

HOOC

CH = OH-OH

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Dye 12

οoc

-CH = CH-CH =

Dye 13

= GH-CH

Dye 14 "

ιτο ·

-.- ■ (CIIo) ₅ SOsH. V,

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IHSPECTSD

Dye .15

C H-

Dye 16 '

OH = OH-

Dye 17

= OH - OH = OH

ce.

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Dye 18

OK-OH = OH-

(CHj ₃ ) SO

OH = 0H-

Dye 20

OH-O II = C H

O C * OH

G3iXi

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ORIGINAL INSPEOTH)

2U-0540

Dye 21

C)

CJ ₂ H ₅

ν / ΐ

J> = CH-CH =

CH

dye

Fs

} = OH-CH = CH- l / · /.

CJ ₂ II ₅

CH-GH

C ₂ H ₅ K

Dye -f 8

2 0 9 8 0 8/1756

Often KSINAL INSPECTED

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Dye 24

(CHj ₃ ) 5SO5

SO ₂ KH ₂

Dye 25

Cl

O ₂ H

(OH ₂ ) SSO3

dye

- CH «« OH

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-CH = CK-CH =

Partstoff 28

CH-CH

Dye 29

-Cn = CH-CH

Oils

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Dye 30

Cl

a.

Dye 31

O Oil's

· '. · ") - CH-C-O JI ~ /

s.-V . *

OHgOH ₂ SOs

Dye 32

^

ce

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* - ^ -. Λι INSPECTED

2U-054Q

dye

Dye H ₃ O

Dye 35 EO

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Dye 36

Oh

Dye 37 · ■

C E

N (CoEs) ₃ '

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The seisibilizing dyes of the invention will be in the Ag GlBrI emulsions preferably in concentrations from 0.005 to 20 g / mole of silver halide is used.

The addition of the sensitizing dyes to the AgClBrI emulsion can be carried out by methods known per se. The sensitizing dyes are usually used for this purpose dissolved in water, methanol, ethanol or other organic solvents and added in the form of a solution water-insoluble sensitizing dyes specified in British Patent 1,154,781 can be used as substances be added in dispersion in an 'aqueous colloid.

According to the invention, gelatin AgClBrl emulsions used. However, the gelatin can also be completely or partially replaced by resinous materials or cellulose derivatives that do not interfere with the photosensitive materials result.

The photographic emulsions within the scope of the invention can chemical sensitizers, anti-fogging agents, stabilizers, film hardeners, plasticizing development promoters, Contain air anti-fogging agents or color couplers if desired.

The color couplers to be used in the context of the invention are from US Pat. No. 2,600,788, the British patent 904 852 and Japanese Patent Publication 6031/65.

Examples of usable color couplers are given by the following chemical formulas.

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O -

3-0

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to

. · - '2UOSAO

O O i! O O O Ci
»—I • P3
O - -O O O

Γ ^ I <

I O

H Ά . : ■ · ■ H O : ^W SO +? O -O • ^ ¹ ! 02
M. ι-Μ
O P? I]
^Λ !>. υ Cl O * - ■ -. ö - • . '■ .. ■. ι " in '. a '.' ■ "·. S» : x ^V : " ^: " ■ '■■' .V. W '■ O "" '"' .. '·· ■' ■ \ - ° - ". O '■' ■ ·· ■ .. "''. ',' ·. · · O 5- / Λ. . ■ '■■ "■■ - ■ m
· ■ - ■ - ■ -. ■ ·. - w
* ■ · - ■ ■ · ·

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■ Ρ H

O O

209808/175 6 ' ORfOlNAL INSPECTED

co

crj

W <o

W ο

Ii

W o— ο

O O

O · OJ

WHERE

W.

2H0 5 4Q.

-O

INSPECTED

ö > ν O Ρ-ί
approx - ο rl O • .K ο - O ti

■ j ■ - " • O •• "■ i O O ο O O ö ; 7 O . · - * ii {J O .ο t

HO ri SO

• -HiU2 ^f iilt-i: "fa%

/ 1756

OWQtNAL INSPECTED

H .rl

ic . *. ο ο oi K

98Ό87ί75 6;

INSPECTED

, - of - 209808/1 7

OfHOtNAL INSPECTED

The photographic emulsions according to the invention can be applied to suitable supports, for example glass, films made from cellulose derivatives, films made from synthetic resins, synthetic papers, baryta papers and photographic papers covered with polyolefin coatings are applied.

An adsorption isotherm is shown in FIG. 1 and in Pig. 2 is the spectral transmittance curve of a glass filter.

example 1

The emulsions A and B prepared according to the following procedures became the sensitizing dyes added and the resulting mixtures applied to a cellulose base aus.Triaeetylcellulose.

Emulsion B was prepared under the same conditions as emulsion A, but at the time Liquid III, which did not contain any potassium iodide, was applied to the formation of the silver halide »

Emulsions A and B were digested to optimum speed. Both emulsions A and B had sensitivities almost of the same order of magnitude.

Preparation of emulsion A ;

Γ Gelatine 20 g liquid J _{Natrluihctllorld 1 | 0} g

(800 ml of water

Liquid (silver nitrate 100 g ¹¹ (water to 600 ml

Γ 10 ίί aqueous solution of liquid J Potassium iodide 10 ml

¹¹¹ / potassium bromide 21 g / ater at 600 ml

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aqueous 1 η solution
of sodium carbonate 7.0 ml Water au 1600 ml gelatin 180 G

liquid
IV

Liquids II and III were, however, added simultaneously or separately to the fluid I at 6G ⁰ C in 20 minutes. The pH of the obtained liquid was adjusted to 4.0 at 60 ⁰ C and the flocculating agent llekala added for precipitation. The precipitate was then washed with water and mixed with liquid IV and then with V to prepare the silver halide dispersion. The emulsion obtained was digested until the optimum sensitivity at 55 ⁰ C for about 60 minutes.

. The surface material produced by applying the emulsion to a support was exposed to light through 'sin Fuji K.-Filter Hr.3, a product of Fuji Photo Film Co. Ltd., and exposed a wedge for one second using a tungsten lamp as the light source. The Fuji K. filter No. 3 is a yellow filter that transmits light with a wavelength longer than about 510 m / rev.

The exposed test material was developed at 20 ^° C. for 4 minutes with the following developer.

Developer's instructions;

Methol 0.31 g

I Sodium Sulphite Anhydride 39.6 g

Hydroquinone 6.0 g

lithium carbonate anhydride 18.7 g

Potassium bromide 0.96 g

Citric acid 0.68 g

Metapotassium bisulfite 1.5 g

Water to 1 1

209808/1756

2U05A0

The test material was fixed, washed with water and dried and finally the optical density the same determined with a densitometer, the results being shown in Table I.

The yellow sensitivity of emulsion B was taken as the standard of 100 and the sensitivity of Emulsion A is given as a relative value to this standard.

Table I.

Digit of, dye
and amount added
(mg / mole silver halide) Emulsion A fog Emulsion B ITebel Dye 1 (0.115)
Dye 2 (0.101)
Dye 3 (0.184)
Dye 4 (0.696)
Dye i (0.493)
Dye 6 (0.086)
Dye 7 (0.118)
Dye 8 (0.120)
Dye 9 (0.088)
Dye 11 (0.436)
Dye 12 (0.062)
Dye 13 (0.011)
Dye H (0.475)
Dye 15 (0.125)
Dye 16 (0.343)
Dye 17 (0.041)
Dye 18 (0.046) Yellow sensitivity
opportunity 0.04
0.04
0.04
0.04
0.04
0.04
0.04
0.04
0.05
0.04
0.04
0.04
0.04
0.04
0.04
0.05
0.04 Tingling
opportunity 0.04
0.04
0.04
0.04
0.04
0.04
0.04
0.04
0.05
0.04
0.04
0.04
0.04
0.04
0.04
0.05
0.04 245
330
'174
165
224
234
19.5
186
159
126
120
118
120
142
120
151
135 100
100
100
100
.100
100
100
100
100
100
100
100
100
100
100
100
100

2 0 9 8 0 8/1756

Table I (continued)

Numeral of the dye
and amount added
(mg / mole silver halide) 18 ' (0.046) Emulsion A fog Emulsion E. fog dye 19th (0.015) Yellow sensitivity
opportunity 0.04 G-elf sensitivity
lichlceit 0.04 dye 20th (0.014) 141 0.04 100 0.04 dye 21st (0.025) 118 0.04 100 0.04 dye 22nd (0.029) 120 0.04 100 0.04 dye 23 (0.025) 132 " 0.04 100 0.04 dye 24 (0.025) 141 0.04 100 0.04 dye 25th (0.060) 135 0.04 100 0.04 dye 26th (0.071) • 151 0.04 100 0.04 dye 27 (0.009) 159 0.04 100 0.04 dye 31 (0.083) 166 0.04 100 0.04 dye 32 (0.086) 120 0.05 100 0.05 dye 33 (0.041) 124 0.04 100 0.04 dye 34 (0.075) - 126 0.05 100 0.05 dye 35 (0.081) 115 0.04 100 0.04 dye 36 (0.151) 141 0.04 100 0.04 dye 37 (0.006) 138 0.04 100 0.04 dye 5 « (0.060) 145 0.04 100 0.04 dye "112 0.04 100 0.04 110 100

Example 2

The dyes were added to the emulsions C and D prepared in accordance with the following instructions: stirred for 20 minutes and then the coupler dispersion substance given and continue to be a film hardener and

209808/1756

a coating auxiliary added and the resulting mixture applied to a paper covered with a polyethylene coating.

The emulsion D was prepared under the same conditions as Emulsion G, but the liquid I, however, was free of potassium iodide _s was applied of the silver halide at the time of training,

Emulsions C and D were up to optimal Sensitivity digests. Both emulsions C and D had Sensitivities of practically the same order of magnitude.

Preparation of emulsion C:

gelatin 20th G G $ 10 aqueous
Potassium;] odide solution 5 ml ml liquid Potassium bromide 49 G G
ral ¹ Sodium chloride 15th G ral Cadmium chloride-5 / 2-
Hy dra t 3A ml Water too 1200 G liquid
II C silver nitrate
IV / as s he too 100
800 liquid CIn sodium carbonate 7th III. / Water too 1600 liquid
IV gelatin 180

Liquid II was added to liquid I at 55 ° C. over 15 minutes. After 5 minutes at 55 G had been digested, the resulting liquid became on

209808/1756

Cooled 4O ⁰ C and Rait a precipitating -vermischt to AusiSLlung. The resulting precipitate was washed with water, mixed with the liquid III and then with the liquid IY and the silver halide dispersion was obtained again. The emulsion obtained was digested at 55 ° C. for about 60 minutes for optimum sensitivity.

The test material prepared by applying the emulsion to a support was dried and started Light through a Fuji K, filter ITr. 17 and a wedge of light exposed for 2 seconds using a tungsten lamp was used as a light source. The No. 17 Fuji K. filter is a green filter with those shown in FIG Properties.

After exposure, the test material became the Stages of color development with a color developer, a Fixing bath treatment, .. water washing, bleaching bath treatment, Water washing, film hardening bath treatment, water washing and Subjected to stabilizing bath treatment in this order.

Subject to these levels became the optical density of the test material determined with a densitometer and obtained the results shown in Table II.

209808/1756

ORIQINAI. INSPECTED Tabel

II

O 1 CO t- CO I. O OO «-4 cn cn

dye
(mg / mole silver
halide) Coupler dispersion
substans (g / mole Sil
berhalide) emulsion 0 fog Enmlsion D dear el Dye 1 (0.230) - Green sensation
opportunity 0.04 Green sensation
lightness 0.04 Dye (0.230) (2400) 100 0.04 100 0.04 Dye 2 (0.101) - 79.5 0.04 31 0.04 Dye (0.101) (2400) 100 0.04 100 0.04 Dye 4 (0.174) - 91 0.04 38 0.04 ■ Dye (0.174) (2400) 100 0.04. 100 0.04 Dye 6 (0.171) - 74 0.04 20th 0.04 Dye (0.171) (2400) '100 0.04 100 0.04 Dye 8 (0.240) - 72 0.04 23 0.04 Dye "(0.240) (2400) 100 0.04 '100 0.04 Dye 10 (0.088) - 83 0.04 42 0.04 Dye (0.088) (2400) 100 0.04 100 0.04 ·. dye 16 (0.137) κ ... * " 96 .0.04. 52 0.04 Dye (0.137) (2400) 100 0.04 100 0.04 Dye 20 (0.014 ' - 98 0.04 76 0.04 Dye (0.014] (2400) 100 0.04 100 0.04 Dye 5 '(0.115! - 98 0.04 87 0.04 Dye (0.115! (2400) 100 ' 0.04 100 0.04 98 90

-C

X-.

■ O

cn

2H0540

The green sensitivity of the emulsion containing the dye was taken as a standard of 100 and the green sensitivity of the emulsion in the presence of the coupler was compared with the value relative to it Standard specified.

Example 5

To the emulsions C and D according to Example 2, sensitizing dyes were added and the resulting dyes Emulsions each applied to baryta paper. -

The test materials made from these emulsions were exposed to light for 1/100,000,000 seconds through a VY ~ 50 color glass filter from Tokyo Shibaura Electric Company and a light wedge using a Mark VII actinometer from EG & G Company, United States. The colored glass filter VY-50 is a yellow filter that transmits light with a wavelength of about 500 m / rev.

The exposed test materials were developed with the following developer for 20 minutes.

Developer's regulation:

MeV.ol 3.1 g

Sodium Sulphite Anhydride 45 g

Hydroquinone 12 g

Sodium Carbonate Anhydride 79 g

Potassium bromide 1.9 g

V / ater to 11

After the! Fixation, water week and drying was done the reflection density (concentration) is determined and dio in Results listed in Table III were obtained.

209808/17 5 R.

Table III

Dye (mg / mol
Silver halide) Emulsion C lever Emulsion D lever Dye 28 (0045)
Dye 29 (0088)
Dye 30 (0090) Tingling
opportunity 0.04
0.04
0.04 Yellow sensitivity
opportunity 0.04
0.04
0.04 120
148
130 100
100
100

The sensitivity was determined in the same manner as in Table I.

209808/1756

Claims (5)

Claims 1 "Green sensitized silver iodobromochloride photographic emulsion, characterized by comprising a J-band sensitizing type dye and a mixture be contains silver halide mass, the AgI in the range from 0.1 to 5 MoI-7S and AgBr in the range from 15 to 95 MoI-J contains, with the exception of a content of AgI of 5 Mo 1- $ and an AgBr content of 95 mol #. 2. Emulsion according to claim 1, characterized in that that the: J-band sensitizing type dye is a compound represented by the following general formulas I, II, III, IV, V or VI is: W -WY V CH- where R is an hydrogen atom or a lower alkyl group, Y ₁ and Y- is a hydrogen atom, a lower alkyl group, a halogen atom, a hydroxyl group, an alkoxy lip, an araino group, an acylamide group, an acyloxyl group, a carbalkoxy group or an alkoxycarbonylamino group , Yp and Y, - a hydrogen atom, a lower alkyl group, a halogen atom, a hydroxyl group, an alkoxyl group, an amino group, an acylamide group, an acyloxyl group, a carbalkoxyl group, an alkoxylearbonylamino group or a phenyl group, where the radicals Y. and Y2 or Y. and Y _{1 can be} a methir chain such that Y ₁ and Yp or Y. and Y 209808/1756 2U-05AQ may be condensed with one another to form a benzene ring, Y, and Yg may be a hydrogen atom or a hetnine chain, so that ' J, and Yg or Yg and Y- may be condensed with one another to form a benzene ring, except that the pairs Y, and Yp as well as Yp and Y. form benzene rings at the same time, with the exception that both pairs Yg and Y ~ and Y ₁ - and Y, simultaneously form benzene rings, R. and Rp alkyl groups, where at least one radical R ^ or Rp is an alkyl group with a carboxyl group or an alkyl group with a sulfo group, X is an anion and η denotes the numbers 1 or 2; (ID γ ι where Z is a radical 0 or a group ^ CyD »where R. and Rr represent an alkyl group, R represents a lower alkyl group or an allyl group, Y _{7 represents} a hydrogen atom or a halogen atom, Yo represents a hydrogen atom, a halogen atom, an alkoxyl group, an amino group, an acylamide group, an acyloxyl group or an alkoxycarbonylamino group, R "represents a hydrogen atom, a lower alkyl group, a halogen atom, a hydroxyl group or an alkoxyl group, Y ₁₀ a hydrogen atom, a lower alkyl group, a halogen atom, an alkoxy group, a phenyl group, a carboxyl group, an alkoxycarbonyl group, a cyano group or a trifluoromethyl group, Y ... a hydrogen atom or a hethine chain which can form a benzene ring _{on condensation with Y 10,} 209808/1756 where the radicals Yq and Yq can be a methine chain which can form a benzene ring on condensation with one another, but not both pairs Yq and Y ^ ₀ and Y ^ ₀ and Y _{11 can} simultaneously form ben ^ ol rings, and R ^, Rg, X and η have the same meanings as in Pormel I; l (in) wherein R. and R ^ are an alkyl group, Ί, ^ ^{un (} 3 · Y-13 is a hydrogen atom or a halogen atom, Y ^, and Y, c is a hydrogen atom, a halogen atom, an alkoxy group, an amino group, an acylamide group, a Acyloxyl group, an alkoxycarbonylamino group, a cyano group, a trifluoromethyl group, an alkylsulfony group, a sulfamyl group, an alkylaminosulfonyl group, a morpholinosulfonyl group or a piperidinosulfonyl group and R .., Rp, X and 11 have the same meanings as in formula I; > _-_ CH-C- CH 209808/1756 2H-054Q where Xg is a hydrogen atom, a halogen atom, Y. "a" hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a phenyl group, Yg is a hydrogen atom or a methine chain which can form a benzene ring on condensation with Υ * η, Yq and Y ₂ Q denotes a hydrogen atom, a halogen atom, a lower alkyl group or an alkoxy group and R, R ^, R ₂ , X and η have the same meanings as in formula T; wherein Y p ^ is a hydrogen atom, a hydroxyl group, a lower alkyl group, a halogen atom or an alkoxy1 group, Y _{22 is} a hydrogen atom or a lower alkyl group, Yp-? sin a hydrogen atom, a lower alkyl group, an alkoxy group, a hydroxyl group or a phenyl group and R., Rp, X and η have the same meanings as in Pormel I and 209308/1756 where Yp4 ^{and Y} ?5 ^{denote a} hydrogen atom, a lower alkyl group, an alkoxy group or a halogen atom, and R-, R2 >> X and η have the same meanings as in formula I. 3. Emulsion according to claim 1 or 2, characterized in that the amount of the dye in the range of 0.005 up to 20 g per mole of silver halide. 4. Emulsion according to claim 1 to 3, characterized in that the mixed silver halide composition contains the AgI in an amount in the range from 0.1 to 2.5 Mo1- $ and the AgBr in the range from 30 to 90 NoI-fo . 5. silver halide photographic light-sensitive material; consisting of a support with at least one layer thereon which is a photographic Emulsion n & ch claims 1 to 4 contains, 209808/1756