DE1906010A1 - Color photographic silver halide emulsion - Google Patents

Description

Konishiroku Photo Industry Co., Ltd.

1-10, 3-Chome, Nihonbashi-Muro-machi, Chuo-ku, Tokyo, Japan

Color photography marriage silver halide emulsion

The present invention relates to a color photographic, light-sensitive halogen silver emulison which is capable of forming a color image after color development. In particular The present invention relates to a color photographic emulsion containing a pyrazolone derivative as a magenta color former contains.

The present invention accordingly provides a color photographic Halogen silver emulsion, which is characterized in that it contains at least one color former of the general Formula I together with at least one compound of the general formulas II and III

Il I

N CO

x ₃

II

-2-

009833/1726

F CH-X ₅ III

worm

] L · an unsubstituted or substituted alkyl, acylamino or sulfonamido group,

XJ, X ₂ and X ,, which can be the same or different, represent hydrogen, an unsubstituted or substituted alkyl group, halogen, an acylamino, unsubstituted or substituted alkylcarbamoyl, sulfonamide, unsubstituted or substituted sulfamoyl, alkoxy or aryloxy -Group stand,

A and B stand for -COR ₂ , -COOR ₂ *, -CONHR ₂ "or -CN,

R ₂ , R ₂ ¹ , R ₂ ^M i X ^ and X _{5 represent} a substituted or unsubstituted allyl, alkyl, aryl, cycloalkyl or aralkyl group,

F is an atom or radical that forms a

Pyrazolone ring is required contains.

Based on various studies on photographic silver halide emulsions, which contain a color former, it has been found that a light-sensitive photographic material, that with a photographic silver halide emulsion was prepared, which has only a color former with low coupling activity, when treated with an im consisting essentially of a p-phenylenediamine derivative Developer solution provides good linear gradation. The development / winding speed is due to the low Coupling activity is decreased and the density is insufficient. As a result, the contrast of the obtained image is poor, and sufficient photographic sensitivity cannot be obtained. It is proposed to avoid these disadvantages to increase the amount of the color former and the silver halide, or to increase the thickness of the emulsion layer.

009833/1726

However, it is generally known that these two attempts to Improvement entail considerable disadvantages, and that the above-mentioned disadvantages are not thereby more satisfactory Way can be eliminated. In addition, the increase in the amount of the color former and the silver halide has a significant effect Increase in the viscosity of the emulsion, and the coating of a substrate with such an emulsion is difficult. In addition, such an emulsion is very foggy and leads to deteriorated stability the photographic properties. On the other hand, an increase in the thickness of the emulsion layer leads to a reduction in the sharpness of the images obtained due to halos, irradiation and other factors

In view of this, is a combination containing a color former with low coupling reactivity and a color former with a relatively high coupling reactivity, has been proposed. The disadvantages of the above-mentioned prior art methods are overcome by such a combination eliminated to some extent. However, by combining two or more different color formers, a Mixing of the developed colors causes an undesirable color shift to occur. That's why it's impossible to use this emulsion for color photography.

According to the present invention it has now surprisingly been found that at least one color former of the above general Formula I, which has a low coupling reactivity, in Combination with at least one of the compounds of the general formulas II and III with an oxidation product of a p-phenylenediamine derivative to form a colorless one React coupling product are added to the photographic silver halide emulsion. The emulsion obtained suffers not under a change in the spectral absorption characteristics of the developed dyes and, this is special important, the sensitivity and the gamma values are also

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neatly greatly increased. Due to the fact that the color photographic Halogen silver emulsion according to the invention Has increased sensitivity and increased gamma values is a small amount of color former is sufficient and the viscosity the emulsion is reduced. Accordingly, the application of the emulsion to a vehicle can be carried out easily will. In addition, these emulsions are safe from fogging and the thickness of the emulsion layer can be reduced will. With such an emulsion, there can be obtained a color photographic light-sensitive material which is improved Shows sharpness of the image obtained.

Typical color formers of the general formula I are the following compounds:

-5-

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CH, - σ

J I!

CH,

N CO

NHCOCH -

CH ^ COOH

(1-2) O ₁₆ H ₃₃ -

CHCONH - C H

j N CO

CHCONH

CH ₂ COOH

CH,

CONH - C

CH ₂

N CO

V /

ΊΓ

Cl

- Q -

009833/1726 '0flK3MAL INSPECTED

(1-4)

- C -
Il I.
J Γ 1906010 - 6 - II
N fy ~ com CHCONH
ι - CH ₂ ■ SO ₃ H CO

OCH,

(1-5)

³ 18 ^H 35 "

CONH - C-

Il

CH.

! ^£ co

CHCONH CH ₂ COOH

OCH

(1-6)

(1-7)

CHCONH CH ₂ COOH

CONH ■ - C CH.

N CO

! ■ 8 * 35 "

<V-CONH - C

Γ

CHCONH CH ₂ COOH Cl

CH,

I'CO

-Cl

009833/1726 Often GINAL INSPECTED

(1-9)

SO ₂ NH - C

HOOC - CHCH ₂ CQNH C ₁₈ H ₃₇

u c

CH

co

(I-IO) C ₁₆ K ₃₃ - CHCONH -

C "CM '

N CO

■ V

SO ₂ N (CH ₃ ).

(I-II) C ₁₆ H ₃₃ - CHCQSH - C CH ₂

CO

K C

(X-12) HOOC - CH ₉ - C

CH.

I C

CO

'V

KHCOCH ₂ - CH - 009833/1726

COOH

-8th-

ORIGINAL JNSPECTEO

• *- 1

- 8 Typical compounds of the general formula

II are the following:

(II-l) CN-OH-CO . CH,

COOH

) ■

C ₁₀ H,

(II-2) ClT-CH-CONH- / ~ \ | ^{18 37}

CH,

SO ₅ H

(II-3)

CO-CH-CONH

SO ₅ H

CH, C0 - CH - CONH- / ~ VN < ¹ 5 ι \ _{s =} / X _0H

CH,

SO ₅ H

(II-5) HOOC - CH - CH ₂ CONH - / _ Λ-CO - CH -

CONH-

'CH,

(II-6)

CO-CH-CONH

i CH ₂ -CH = CH ₂

009833/1726

Typical compounds of the general formula III are as follows:

- CHCH,

(HI-I) Ci ₇ H ₅₅ - C (III-2)

(III-3)

BT CO

SO, H

^C 15 ^H 31

CONH - C

CHCH ₅

N CO

- C

SO ₅ H

CHC ₂ H ₅

N CO

V /

(III-4)

CHCH ₂ Cl

N CO

SO, H

33/1726

(III-5)

- ίο -

- σ

CHCH ₂ COOH

N, CO

(III-6) (HO) ₂ H ₅₅ C ₁₇ - C-

CHCH,

N CO

\ "/

σι

(111-7)

NH
CO

CH ₉

I ²
CH-COOH

^C 18 ^H 37

- σ-

CH ₂ Cl CH

N CO

(III-8)

-CONH

- σ

CH-CO

/ Λ

11 -

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(III-9)

- OH OH,

(III-1O)

σ Il

CH -

OH,

It is well understood that the color formers of the general formula I and the compounds of the general formulas II and IH ₁ which are used according to the invention are not restricted to the above examples. In particular, the present invention also includes the alkali metal salts or the ammonium salts of sulfonic acids or carboxylic acids of the compounds of the general formulas I and II or III

You can add at least one color former of the general formula I and at least one of the compounds of the general formulas II and III to the photographic emulsion directly in the form of an aqueous alkaline solution, e.g. in sodium hydroxide. It can also be carried out in such a way that a dispersion is prepared in that the color former of the general formula I and the compounds of the general formulas II and III in a low-boiling organic solvent such as butyl alcohol and butyl acetate and in a high-boiling one organic solvents such as dibutyl phthalate, which

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holding solutions with one containing a surfactant Gelatin solution is mixed and the mixture is then treated in a colloid mill. Alternatively, can the addition takes place by means of known dispersion methods Each of the compounds of the general formulas II and III is used in a molar ratio of 0.05 to 1 to the color former general formula I used · Particularly effective is a molar ratio in the range from 0.1 to 0.5 »

For the production of the photographic emulsions according to the invention can use the various halogen silver emulsions such as Silver chloride, silver bromide, silver iodide and silver chlorine - bromide emulsions can be used. These emulsions can a chemical sensitizer such as a sulfur, reductive or noble metal sensitizer and an optical sensitizer They can also contain various additives, for example antifoggants, stabilizers, Anti-yellowing agents, development accelerators, hardeners, coating aids, etc.

When the optically sensitized emulsions as two layers can be applied to the same carrier, the color former of the general formula I and the compounds of the general formulas II and III are added to each of the two emulsions will.

The invention will now be explained further by means of the following examples, the specified parts being parts by weight.

example 1

To 100 parts of a light-sensitive grelatin silver bromoiodide emulsion, which has been prepared in the usual manner and contains a green-sensitive optical sensitizer becomes a 5% aqueous alkali solution of the color former (1-7) and one 5% alkali aqueous solution of the compound (III-2) or (III-4) given in the amounts shown in Table 1.

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0 0983 3/1726

The emulsion thus treated is applied to a film support. The film obtained is then treated with a developing solution, which is the main color developer, for 10 minutes at 20 ° C Contains Ν, Ν-diethyl-p-phenylenediamine. Afterward is bleached and fixed. The increase in density is given in Table 1 by means of the photographic Gamma value measured using green light density. The emulsions according to the invention show a remarkable one Increase in gamma values.

Table 1

Color former I Compound III W ^ ^^ ΊΓΥΙ Wl ^^ (Parts) (Parts) 1-7 (21) III - 2 (0) 0.29 ¹¹ (21.5) W ( ^W ) 0.50 »(22) N ( ^M ) 0.32 ^tt (20) ^M (1) 0.36 Il ( ^W ) "(1.5) 0.39 η (η \ ⁿ (2) 0.53 It ( ^M ) III - 4 (1) 0.33 H ( " ) "(1.5) 0.37 It f It \
) * (2) 0.51

Example 2

As described in Example 1, a similar film is produced in that a 5 # aqueous alkali solution of the color former (1-7) and a 5 # aqueous alkali solution of the Ter bond (III-1) in the amounts shown in Table 2. Die Tärben und der Farbbilders (III-1) be used. The film obtained is then treated in the same manner as described in Example 1. The measured gamma values are given in Table 2. From Table 2 it can be seen that the emulsions according to the invention show a remarkable increase in the gamma values.

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Table 2

Color former I Compound III • gamma (Parts) (Parts) 0.36 1-7 (21) III - 1 (0) 0.38 "(21.5) tt (") 0.40 ¹¹ (22) N ( ^U ) 0.46 »(20) ⁿ (1) 0.50 H ( " ) ^u (1 · 5) 0.68 W (") ¹¹ (2)

Example 3

Three mixtures, each containing 1 part of the color former (l ° -8) and 1, 1.5 or 2 parts of the compound (III-5) _? are dissolved separately in 3 parts of ethyl acetate each time with warming.

1 part of dibutyl phthalate is added to each of the solutions obtained.

The solutions thus obtained are mixed with 10 parts of an aqueous 10 $ gelatin solution and then passed through a colloid mill directed to produce a color former dispersion. The same amount of this dispersion as that used in Example 1 is added to an emulsion that contains an appropriate amount of gelatin in order to obtain a finished total emulsion, which contains the same amount of gelatin as that of Example 1. The photographic gamma values associated with one of them The films produced and treated in the same manner as in Example 1 are shown in Table 3.

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Tackle He 3

Color former I
(Parts) Compound III
(Parts) Gramma 1-8 (21) III - 5 (0) 0.30 "(21.5) N (") 0.31 "(22) M ( ^M ) 0.33 * (20) " ( 1 ) 0.37 N ( ^N ) "(1.5) 0.42 N ( ^N ) * (2) 0.57

It can be seen from Table % that the emulsions of the invention have remarkably increased gamma values.

Example 4

Emulsions analogous to those used in Example 1 are prepared by adding 5% aqueous alkali solutions of the color former (1-7) and 5% aqueous alkali solutions of the compound (II-1) in each case in the table 4 are added. The photographic gamma values resulting from Films produced and treated as described in Example 1 are shown in Table 4.

Table 4

Compound III Ποητηύ Color former-1 (Parts) % Tcs ^ U ^^^ & Cl (Parts) II - 1 (0) 0.26 I - 7 (21) M (") 0.27 "(21.5) M (*) 0.28 "(22) " ( 1 ) 0.30 "(20) "(1.5) 0.33 R (*) "(2) 0.37 M ( ^M )

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From this table it can be seen that the emulsions according to the invention have exceptionally increased gamma values.

Example 5

Emulsions analogous to those used in Example 1 are prepared by using 5 # aqueous alkali solutions of the color former (1-7) and 5 # aqueous alkali solutions of the Compound (II-5) are added in the amounts indicated in each case in Table 5. The photographic gamma values at Films produced therefrom and treated in the same manner as described in Example 1 are measured in Table compiled.

Table 5

Color former I Compound II 0.17 (Parts) (Parts) ■ 0.18 I - 7 (21) II - 5 (0) 0.20 "(23) N (") 0.22 ⁿ (25) ⁿ (") 0.24 . "(20) " ( 1 ) 0.27 H ( ⁿ ) (3) n / mV "(5)

In the above examples, the present invention has been completed to that end explains that the combination of a color former and another compound was used. However, it is it has been observed that the same effects are obtainable when a combination of, for example, the color former (1-1) and compounds (III-1) and (III-2) is used.

Claims

009833/1726

Claims (6)

Claims; Iy color photographic silver halide emulsion, thereby characterized in that they contain at least one color former of the general formula I together with at least one of the compounds of the general formulas II and III CH - X ₄ II i oh - X ₅ in wherein E _{1 is} an unsubstituted or substituted alkyl, acylamino or sulfonamide group, X ₁ , X ₂ and X ,, which can be identical or different, represent hydrogen, an unsubstituted or substituted alkyl group, halogen, an acylamino, unsubstituted or substituted alkylcarbarnoyl, sulfonamide, unsubstituted or substituted sulfamoyl, alkoxy or aryloxy -Group stand, A and B stand for -COR ₂ , -COOR ₂ ¹ , -CONHR ₂ "or -CN, Ent Ro'i Ro "i Xi and X ₁ - a substituted or un- 2 * 2 'd. ¹ 4 ρ substituted allyl, alkyl, aryl, cycloalkyl or Aralkyl group mean -18- 009833/1726 F is an atom or radical that forms a Pyrazolone ring is required contains. 2. Halogen silver emulsion according to claim 1, characterized in that that they are a compound of the formula as a color former ° 18 ^H 35 CHCG
CH ₂ COOH COIiH ~ C egg CH co Cl Cl in combination with a compound of the formula (1-7) - CONH - CHCH or O ₁₇ H ₃₅ CHCH ₂ Eq CO (III-2) (III-4) -19- 009833/1726 contains. 3. Halogensilberemulaion according to claim 1, characterized net that they have a color former of the formula (I-?) in combination with a compound of the formula 17 35 O " CO (111-1) SO ₃ H contains. 4. Halogen silver emulsion according to claim 1, characterized in that net that they have a color former of the formula -COHH - C Il CH ₀ \ ² CO ^CHOOliH C ₂ H ₅ (1-8) Cl I Cl ^tC 5 ^H 11 egg in combination with a compound of the formula -20- 009833/1726 C ₁ "Η", - - C GHCH ₀ COOH Ii ίο < ^IJI - ⁵ > contains. 5. Halogen silver emulsion according to claim 1, characterized in that it contains the color former of the general formula (1-7) in combination with the compound of the formula CH - CH - CO vV / - NHCOCH ₂ CHC ₁₈ H ₅₇ (HI) CH, COOH contains. 6. Halogen silver emulsion according to claim 1, characterized in that that they use the color former of the formula (1-7) in combination with the compound of the formula HOOC - CH - CH ₂ CONH- ^ p - CO - CH - COHH- ^ ^λ > (II-5) C _1R H- ₇ CH-, contains. 009833/1726