DE1547830A1 - Color photographic material - Google Patents

Description

W. 12H8 / 66

Fuji Shashin Movie Kabushiki Kaisha Kanagawa (Japan)

Color photography raw material

The invention relates to a color photographic Material, and particularly to colored cyan couplers, for use in photographic processes.

Almost all cyan couplers that are used in color image formation in color photography, are l-naphthol-2-carboxylic acid derivatives or amino phenol derivatives. In use, these couplers are added to a photographic emulsion, and a long chain one Alkylres ^ in the molecule to prevent the diffusion of the added coupler from the layer which the Coupler to be added, introduced to another, -and more than one carboxylic acid or sulfonic acid group as an alkali-solubilizing group are introduced to make the coupler homogeneous in a photographic emulsion layer to disperse. Often an oleophilic property is also created in the coupler to make it all in one

009808/1382

1547330

organic solvent, hereinafter referred to as "coupler solvent" is called to solve. That obtained when these couplers are coupled with an oxidized color developer Cyan image has undesirable absorption in the blue area and especially in the green area.

US Pat. Nos. 2,449,966 and 2,449,316 describe cyan couplers in which the 4-position of the 1-naphthol-2-carboxylic acid derivative is substituted by an arylazo group, which are suitable for correcting the undesired absorption of the cyan dyes Colored cyan couplers with strong blue absorption are easily made, but it is quite difficult to make colored cyan couplers that have sufficient green absorption to obtain effective masking Green absorption, that is, a cyan coupler colored with magenta is required, and it is required that there is little change in the color of the colored coupler depending on the pH of the color treatment solution, and it is also important that a coupler solvent be used for the addition of the coupler to an emulsion is very disadvantageous, since for the improvement of the image sharpness in a color-sensitive material, the thickness of the emulsion layer should be as thin as possible. While the addition of an in

009808/1382

Alkali-dissolved coupler brings special Voiteile with it to an emulsion layer, the colored coupler generally a notable decrease in sensitivity and create fog in the emulsion. Consequently This enables the production of a highly sensitive, color photographic material, etae with a content a colored coupler, which corrects the undesired absorption of the cyan dye, made difficult.

In Japanese Patent Application No. 62440/63 are colored cyan couplers of the general formula given below

~ CONH -

(Y) _n

described in which R is an alkyl radical with more than 10 carbon atoms, K is hydrogen, eirO / Hticalimetall, an ammonium group or -HNH (R "), where ρ + Q = 3, ρ and q each 0-3 and R ^{n is} a lower alkylrtst are, Y is -COOM, -S0J4 or a carbalkoxy group and η is 1 or 2, it being stated that these

006608/1382

Couplers have a good masking effect. When carrying out further examinations were stained Cyan couplers with excellent properties were found.

The object of the invention is to create alkali · » soluble, magenta-colored cyan couplers that have little color change depending on the pH of the color treatment solution exhibit. Another purpose is to create magenta colored cyan couplers that do not weaken the sensitivity and only induce the appearance of veils to a small extent. According to the invention is a color photographic material provided, in which a l-hydroxy-4-haphthylaio «« »2 ·· naphthanilite derivative of the general formula below

Oh T

CO "

CONH-

009808/1382

is contained in which R is an alkyl group with more than 10 carbon atoms, M hydrogen, an alkali metal, an ammonium group or -HNH (R "), in which ρ + q = 3,

^p q ρ and q are each an integer from 0 to j5 and R ″ one

mean lower alkyl group, and η represent 1 or 2.

As shown in the above general formula, the coupler of the invention has a good solubility in aqueous alkali solution "VSS & pvaiA-äeB since the anilide Kerni · In the 2 'position of the naphthol nucleus a sulfo group as an alkali lös Ii oh mowing group contains. The introduction of a further sulfo group in the naphthylazo group in the 4-position leads to the further improvement of the solubility in aqueous alkali solution. The sulfo group in the anilide core in the 2-position of the naphthol core not only improves the solubility in aqueous alkali solution, but surprisingly causes a shift in the maximum wavelength of the spectral absorption in a film to longer wavelengths, whereby the absorption spectrum for the film to one is improved to a significant extent. In the coupler according to the invention, an alkoxy group having more than 10 carbon atoms is introduced together with the sulfo group in o-position to the amide group in the anilide nucleus in the 2 <*> position of the naphthol nucleus. A special feature of the chemical structure is based on the fact that the coupler according to the invention

009808/1382

resistance to diffusion by a long-chain alkoxy group without sacrificing its excellent effect on the color of colored couplers.

The coupler according to the invention is characterized by the content of a β-naphthylazo group which is substituted by a sulfo group in the 4 «position of the naphthol nucleus. Like in Pig. As shown in I, the colored coupler containing the naphthylazzo groups has greater bathochromic shifts than the coupler containing substituted or unsubstituted phenylazo groups. However, a colored coupler containing an unsubstituted naphthylazo group has an undesirably high balloon absorption and also has a red absorption. This undesirable tendency is lower in the ß-naphthylazo group than in the oC -naphthylazo group. in Pig. I, curve A represents a coupler having a phenylazo group, curve B a coupler having an α-naphthylazo group, and curve C a coupler having a β-naphthylazo group.

The introduction of the sulfo group into the ß-naphthylazo group not only causes a substantial improvement in the

Solubility in aqueous Ällali solution, but in even more pronounced one Way a decrease in the undesirable blue and red absorption to a considerable extent, and therefore leads to an improvement in the spectral absorption in the film

009808/1382

in a remarkable way. I. E. the maximum absorption wavelength in the film is about 20 ΐημ longer * compared with the maximum absorption wavelength in aqueous solution, and the Balau absorption is reduced, being a very desired magenta coloration is obtained without red absorption (see. Fig. 2). The color change caused by the pH the treatment solution is brought about is additionally reduced

JTUs the above is the meaning and the need to introduce a β-naphthylazo group in the ^ position of the naphthol nucleus and the additional Introduction of the sulfo group into the ß-naphtholazo group according to the invention evident. The sulfo group des Coupler according to the invention can be in the form of the free acid or its salt without any difference in their Effect. Examples of couplers used in accordance with the invention are shown below can arrive, but the couplers according to the invention are not limited thereto.

009808/1382

OH

^OC l8 ^H 37

SO ₃ H

(IV)

-. °° 10 ^Η 21

• CONH

8OJ

(V)

OH °° 18 ^H 37

COHE-Q

(m)

IH

CONH -

SO ₃ H

(VI)

ORlGIfSiAL INSPECTED

■ ^OC 18 ^H

^ rr '^ j- COONH \ _ /

WELL

SO H

(VII)

SO ₃ H

OH

cO " ^oonh

Il N

SO

(A)

COOH

. OH

l8 CONH \ _ /

SO ₃ H

HO ₃ S

(VIII)

SO H

OH.

CONH

N Il

so-, H'H H:

OH

^0C 18 ^H 37

·, - CONH

N (B)

SO ₃ H ■,

^0C 18 ^H 37

CONH

Il N

(C)

SO ₃ H

(χ)

ii IV

0098Ö8 / 1382

- ίο -

The couplers according to the invention show excellent Properties when compared with the following control couplers

(A), (B) and (C) of the formulas as given above.

The compound (I) and the comparative coupons (A), (B) and (0) are each weighed in a given amount, dissolved in a small amount of 1N sodium hydroxide solution, with a phosphate solution with a pH of 7.0 to make a solution of 4x10 "^ moles in one pH of 7 * 0 each diluted, indicating their spectral Absorption curves were measured in each case. The curve in which the maximum absorption density is 1.0, is shown in FIG. The spectral absorption curve of the compound (I) in a film shown in the below Example 1 described was obtained ((l) / F), the spectral absorption curve of the compound (i) in aqueous Solution ((l) / W) and the spectral absorption curve of the Compounds (A) in film ((A) / F) are graphically shown in Fig. 2, wherein the maximum absorption density is 1.0.

009808 / 13Ö2
ORIGINAL INSPECTED

1947830

~ 11 -.

From Pig. 1 it can be seen that the compounds (B) and (C) each have a much longer spectral Absorption maximum.as the compound (A), and that the compounds (B) and (C), in particular (B), each have a high blue and red absorption. A comparison from Fig. 1 to Fig. 2 shows that the compound (I) has a lower blue and red absorption in aqueous solution • & Φ- as that of (B) or (C) and that the Spectral absorption characteristic: the compound (I) in a film has a · »about 20 nji longer spectral absorption · maximum «compared to that in aqueous solution, owns. It can be seen from the spectral absorption characteristics of the compound (I) in a film that it Compound the purpose of the invention corresponds better than the compound (A).

The couplers according to the invention are prepared in the following manner.

(I) l-Hydroxy-4 ·· (8 ~ eulfo «ß« naphthy lazo) «2- (2 ~ oo ta-, deeyloxy-5 ^ ulfo) -naphthanllid (formula I)

7 g of 2-naphth | _R larnino-8-sulfonic acid and 1.5 g of caustic soda were dissolved in 50 ml of water. 2 g of sodium nitrite and a small amount of crushed ice were added and the mixture was cooled to 0 ° C. 10 ml of 56% strength sifacic acid were added to this solution with stirring.

009806/1382

BATH ORIGINAL

^ 12 -

18 g of triethylamine salt of 1 "hydroxy-2- (2" pctadeoyloxy-5-sulfo) naphthanilide and 12 g of caustic soda were dissolved in 400 ml of water and cooled to 5 ° C. with Bb. the Solution of the diazonium salt prepared above added dropwise to the solution with stirring, whereupon * after stirring for 1 hour JOO ml of a 36% salt acid and then 500 ml of acetonitrile. The resulting precipitate was filtered, with 200 ml Acetonitrile washed and dissolved in 300 ml of dimethylformamide under, Ephitzen; 500 ml of acetonitrile were added to this solution was added and the resulting precipitate was filtered to obtain the final product

The yield was 15 g (71 f>) and the melting point of the product was above 280 ° C.

4- ·

(II) 1-Hydroxy- ^ 4, 8 "disulf o" ß ~ naphthylazo) -> 2- (2 * octa-

decyloxy-5 "sulfo)" - naphthanilide (formula IT) 9 g of 2 «naphthylamine * 4,8-di-sulfonic acid were used instead of 2 <-naphthylamine-8 "sulfonic acid, as under (I) /. used and otherwise, the same procedure as described in (I) was carried out to prepare the final product.

The yield was 14 g (66 lbs) and the melting point was above 280 ° C.

(III) 1-Hydroxy-4- (6-sulfo * -ß-naphthylazo) -2- (2-dodecyloacy-5 «sulfo) ~ naphthanilide (Formula II)

Instead of 2 »naphthylamino-8 ~ s * lfonic acid was 2-naphthylamino * -6-sulfonic acid and instead of the under (I) 0 0 98-0-3- / 138 2

used triethylamine salt of l-hydroxy ~ 2- (2-octadecyloxy «0-sulfo) naphthanilide were 14 g of the sodium salt of l ~ hydroxy «-2 ~ (2.-dodecyloxy-5 '" sulfo) -naphthanilide used, otherwise the same procedure as described under (I) is carried out for the production of the end product became.

The yield was 12 g (61 %) and the melting point was above 280 ° C.

In the table below are the melting points and nitrogen analysis values of typical examples for Listed couplers according to the invention.

OR

Nitrogen {%)

Formula R ( SO JM) _n g ( ^v C) calculated found

IC ₁₈ H ₅₇ 8-SO, H above 280 4.97 · VT3 ■

^{11 D} 12 ^H 25 6-SO ₃ H "5.52 5.16

III C ₁₈ H ₅₇ I-SO ₅ H ^lr 4.97 4.80

IV ^c i ^{8 H} 57 ^ 8-SO ₅ H "4.53 4.24

VC ₁₀ H ₂₁ 7-SO ₃ H "5.73 5.61

VI C ₁₂ H ₂₅ 3,6-SO ₃ H "4.99 4.67

VII C ₁₈ H ₃₇ 5-SO ₃ H ^tt 4.97 ^, 81

VIII C ₁₈ H ₃₇ 6.8-SO ₃ H ". 4.53 4.32

009808/1382

The invention is illustrated below by way of examples explained in more detail.

Example 1 '

An equivalent amount of 0.5 χ IO ^ mol of the compound (I) in an aqueous 5 $ sodium hydroxide solution was added to 100 g of a red-sensitive iodized silver emulsion containing a panchromatic sensitizer, whereupon with citric acid to a pH of 7 , 0 was set and the product was applied as a coating to a film base and dried to obtain a red-sensitized, color-sensitive material.

The film was exposed to red light through an optical wedge and treated with a developer solution of the following _ specified composition developed. Developer solution

N, N-diethyl-p ~ aminoaniline sulfate ψ g

anhydrous sodium sulfite -2O 4 Sodium carbonate (monohydrate) 50.0 g

Hydroxylamine hydrochloride 1.5 g

Potassium bromide 1.0 g

Water rest to 1000 ml

(pH = 10.8 t 0.1)

The film material was then bleached and fixed using the parameters indicated below

009808/1382

Fixing solutions with the specified composition were used; it became both the undeveloped halogen silver and the reduced silver formed removed to a cyan negative image and a magenta positive image, consisting of the remaining unreacted colored couplers. Bleach solution

Potassium ferricyanide 100 G Potassium bromide 20th S. m
Water rest on
(PH - 1000 ι
■ 6.9 ± nl
0.3) Fixing solution Sodium thlosulfate (hypo) 200 S. anhydrous sodium sulfite 20th G Acetic acid (28 %) 45 ml Boric acid (crystalline) 7, .5 g Potassium alum 20th G Water 'rest on
(PH - 1000 ml
• 4.5 ί 0.2)

The maximum spectral absorption wavelength of the obtained positive image was at 530 nyu, whereby a desired magenta color is displayed. The color of the positive image obtained was almost unchanged, even when passing through a stabilizing bath with a pH varying from 4 to 11 (cf. FIG. 2).

009808/1382

Example 2

An equivalent amount of 1.5 x 10 "^ moles of N ^ n-octadecyl-l ^ hydroxy- ^ sulfo ^^ naphthamide hiatrium salt in aqueous 5 # strength sodium hydroxide solution was added to 100 g of a photosensitive emulsion containing a panchromatic sensitizer. An equivalent amount of 1.0 χ 10 "^ mol of this salt and an equivalent amount of 0.5 x 10" - ^ mol of each of the compounds (I), (IV) and (V) in an aqueous 5 # - Sodium hydroxide solution was added to the emulsion in the same way, as described above in Example 1, in order to obtain red-sensitive materials.

These products were exposed to red light through an optical wedge, developed and fixed, with the vea in The procedure described in Example 1 was carried out to produce both a cyan negative image and a magenta positive image whose densities were measured. The results obtained are compiled below.

009808/1382

Coupler used

Added

lot
(x 10 ~ 3 M ₀ I)

100 g Eraul wave "

sion length d. Pogjtivs ~ Ίφϊ

Maximum relative absorption sensation «- Schiet opportunity he

Nn-octadecyl-l-
hydroxy-4-sulfo "
2-naphthamide
sodium salt 1.5 _ • 100 0.07 ti 1.0 550 98 0.08 Connection (I) 0.5 ψ * mm It + 1.0 Compound (IV) 0.5 528 105 0.06 It Connection (ν) 1.0
0.5 555 100 0.08

The characteristic curve in which the undesired green absorption is masked is shown in FIG. In Flg. j5 the solid line shows the case of using Compound (I) in admixture with N «n« octadecyl-1-hydroxy-4-sulfo-2-naphthamide sodium salt and the dashed line shows the use of N-n «octadecyl-1-hydroxy-4-sulfo-2-naphthamide sodium salt alone. The curves labeled 1 represent the cyan density when using a red filter and the curves labeled 2 represent the cyan density when using a green filter. It can be seen that the coupler according to the invention

009808/1382

has no attenuating effect on sensitivity and leads to slight fogging, and that it has a suitable spectral absorption characteristic.

009808/1382

Claims (2)

Claims 1, color photographic material, characterized in, that it is a color coupler of the general formula below OR CONH -Q SO, M contains, in which R is an alkyl group with more than 10 carbon atoms, M is hydrogen, an alkali metal, an ammonium group or -HNH (R ¹¹ V, where ρ and q are each an integer from 0 to 3 with the proviso that ρ + q = 3, and R * represent a lower alkyl group, and η represent 0 or 2. 2. color photographic material according to claim 1, the/ characterized in that there is a / connection as a color coupler of the formulas given below contains 009808/1382 ^OC 18 ^H 37 II N (D OH Cp. OC H CONH '_ / 37 SO ₃ ¹¹ (IV) CONH SO ₃ H (II) . COBH Il (V) OH OC ₁₈ H ₃₇ CONH - N I (III) .OH Jl SO H 12 ά \ ■ Q SO ₃ H (VI) \ 008608/1382