US3418129A

US3418129A - Color photographic silver halide emulsion

Info

Publication number: US3418129A
Application number: US417243A
Authority: US
Inventors: Kimura Shiro; Yoshida Makoto; Sano Kazuya
Original assignee: FUJI SHOSHIN FILM KABUSHIKI KA
Current assignee: FUJI SHOSHIN FILM KABUSHIKI KA; FUJI SHOSHIN FILM KK
Priority date: 1963-12-27
Filing date: 1964-12-09
Publication date: 1968-12-24
Anticipated expiration: 1985-12-24
Also published as: BE657579A; DE1285314B; GB1018810A

Description

United States Patent 3,418,129 COLOR PHOTOGRAPHIC SILVER HALIDE EMULSION Shiro Kimura and Makoto Yoshida, Odawara-shi, Japan, and Kazuya Sano, University Park, Pa., assignors to Fuji Shoshin Film Kabushiki Kaisha, Kanagawa-keu, Japan, a corporation of Japan No Drawing. Filed Dec. 9, 1964, Ser. No. 417,243 Claims priority, application Japan, Dec. 27, 1963, 38/70,436

The portion of the term of the patent subsequent to 10 Aug. 22, 1984, has been disclaimed 6 Claims. (Cl. 96-100) ABSTRACT OF THE DISCLOSURE 15 integer from 6 to 14 when m is 2, 4, 5, 6 or 7 and n is 14 when m is 3.

This invention relates to light-sensitive silver halide emulsions for color photography and more particularly to a photographic silver halide emulsion containing a protective coupler.

In a conventional color photography using a coupler dispersed in a photographic emulsion, a method of making a coupler water-soluble and incorporating it as a form of an aqueous solution in the emulsion, and a method of making a coupler oil-soluble and incorporating it as a form of an organic solvent solution in the emulsion have occupied important positions. In the second method it is in particular important factors that the coupler has a higher solubility in an organic solvent in use for dispersing and a higher dispersibility during and after applied to a base as a light-sensitive material.

It is therefore an object of our invention to provide a novel coupler having a high solubility in a Water-soluble solvent of high boiling point such as butyl phthalate, otolyl phosphate and butyl phosphate. Another objectis to prevent the ununiformity of applying and the degradation of the final color picture caused by the deposition and aggregation of the coupler during and after the conventional process for producing light-sensitive material comprising, dispersing a coupler solution in a photographic emulsion, followed by applying the emulsion to a base and drying, or even after developing.

We have already found that a compound having the following general structure accomplishes these objects.

where A is a coupling component having at least one ketomethylene group, pyrazolone nucleus, phenol nucleus or a nucleus having phenolic hydroxyl group such as naphthol nucleus and n is an integer from 6 to 12.

Furthermore, we have found that a compound having the following structure not only accomplishes these objects, but represents an excellent property that is not given by the compound described as above,

where A is a coupling component having at least one ketomethylene group, pyrazolone nucleus, phenol nucleus or naphthol nucleus as above and m' is an integer from 2 to 7, n is 14 when m is 3, and from 6 to 14 when m is 2, 4, 5, 6 and 7.

When n is less than 5, the diffusion of the coupler can be observed in the emulsion layer of light sensitive material and when m is 0 or 1, the insuflicient solubility tends to cause a rapid deposition and aggregation during supercooling. When n is 15 or m exceeds 8, the solubility is too low. When n is 14, the solubility may be compared unfavourably with the case of less than this, but the compound can find a practical use in many cases, since the deposition by supercooling is very slow. For example, it is in a very advantageous position particularly when it is adapted for a light-sensitive material which should resist a severe thermal shock or when the coupling A has a property to promote crystallization.

Illustrative of such compounds of our invention is as follows:

NCH CH C oNH-O-C oonzo ONE-O 4 CH (CH2);1C O

NCHzCHzC O-A 60 CH (CH2)14CO CH (CH2)12 (SCH:

3 4 To make clear that the compounds having the general droxy-Z-naphthamide and 10 g. of pyridine, heated to constructure have high solubilities, the comparison with coudensate, left standing for one night and the reactlonmlxplers having a straight chain alkyl group is shown in ture was transferred into a dilute hydrochloric ac1d to Table 1. deposit an oily product. The oily product was washed with TABLE 1.OMPA RISON BETWEEN BRANOHED CHAIN AND STRAIGHT CHAIN Compound (1) (6) (2) (7) Melting point 0.) 64 102 125 168 91 143 so 129 Gram dissolved in butyl phosphate, 100 g. at 25 0 5 0.1 21 4 7o 29 45 5 The compounds 6-9 referred for the comparison are as water, crystallized with the addition of nitromethane and follows: recrystallized from methanol to produce 3 g. of the final 0H product which melted at 64 C.

The homologue thereof could be synthesized in the OONHCHNHZNHCO (0119156113 same manner as above but, in the case of the intermediate branched acid being oily at room temperature, it was employed as it was for the subsequent step after the step of (6) removing ether.

Synthesis of the Compound 2.3 (N propylcapryl- CHQ(CH)IOONHEOH amide)-propionic acid was obtained as 210 g. of an oily N 0 product from 145 g. of methyl-3-propylaminopropionate, 120 g. of triethylamine, 163 g. of caprylic acid chloride I and 60 g. of potassium hydroxide. 27 g. of the acid was reacted with 12 g. of thionyl chloride as in (1) and the product was mixed with 17.5 g. of 3-amino-1-phenyl-5- pyrazolone and 30 ml. of diethyl oxalate, followed by being heated on a hot Water bath to evolve hydrogen chloride. The reaction product was added to 100 ml. of 50% CHKCHZMCONHET aqueous methanol and left standing with cooling to crys- 30 tallize. After filtered, the crystal was recrystallized from N methanol to give 5 g. of the coupler which melted at 01- 01 The homologue thereof could be synthesized in the similar manner. Synthesis of the Compound 3.3-(N-butylpalmitaml ide)-propionic acid was produced by hydrolysis with C1 3 250 g. of potassium hydroxide of an ester obtained from 675 g. of methyl-S-butylaminopropionate, 1140 g. of palmitic acid chloride, 45 0 g. of triethylamine and 5 CHKCHQWC oNH-O-COCHm OM10 liters of ether, recrystallized from methanol to give 1150 I g. of crystal which melted at 56 C. The acid thus reooHe (9) sultant was adequately dried and 187 g. thereof was converted into the oxychloride with 64 g. of thionyl The following examples illustrate the synthesis of the chloride Then, 136 of 3 compounds of our invention and the application thereof P PYD' TY 31010116 was Suspended in 500 of to photographic light-sensitive. mat ri l, tonltrile, to which the oxychloride was added dropwise Synthesis of the Compound l.-174 g. of methyl acry- Wlth heating and stlrrillg- The reaction Pmeeeded With late and 118 g. of propylamine were mixed in a reactor evolving hydrogen chloride gas. After 1 e half equipped with a cooler and the mixture was heated at 70 amount of the acetonitrlle Was removed y distillation, C. on a hot water bath to accomplish the reaction. The 500 of Water Was added thereto, and the mix u reaction product was distilled in vacuo to give 250 g. of Was left Standing and cooling to crystallize, filtered, methyl 3 propylaminopropionate as a fraction at 57 lowed y recrystallization, thereby to give a y 200 C./3 mm. Hg. 145 g. of the resulting methyl-3-propylg which ed a 91 C.

aminopropionate and 120 g. of triethylamine were disy of the homologue of e compound could be y solved in 1.5 liters of ether, to which 246 g. of myristyl h iz d in the im r nn r- It could be Synthesized chloride was added dropwise with stirring and cooling by in he same manner as in (2) but in the case the melting ice. After the addition, the mixture was stirred at room Point f h Pr duct was 10W.

temperature for /2 hour and the resulting triethylamine Synthesis f the Compound 4.-40 g. of the oxychloride was filtered off. The ether solution was adequateoride Obtained in the synthesis of the Compound 3 1y washed with water, dried and distilled in vacuo to give so was a d d p at room temperature to a p 290 g. of methyl-3-(N-propylmyristamide)-propionate sion of 28 g. of 4-aminobenzoylaceto-2-methoxyanilide which boiled at 201-3" c./1.5 mm. 290 g. of the resulting and 13 gf triethylamine in 300 of acetone, refluxed ester and an alcoholic solution of 60 g. of potassium hyr a While, transferred into water to separ e an oily droxide were mixed, heated for 1 hour, refluxed and disproduct and the oily product was recrystallized from tilled off the alcohol. To the residual solution, were added nitr ethane and Subsequently from ethanol. Yield: 15 g., 120 ml. of concentrated hydrochloric acid and 100 ml. M.P. 80 C.

of Water to separate an acid, which was extracted with 1 The synthesis of aminobenzoylacetoanilide derivatives l ter of ether, dried by sodium sulfate anhydride and discould be carried out in the same manner and, in addition, tilled to remove the ether therefrom. The product was carried out as the following example.

recrystallized from methanol to give 205 g. of 3(N- Synthesis of the Compound 5.3-(N-octylmyristam-' propylmyristamide)-propionic acid which melted at 45 ide)-propionic acid chloride was produced by reacting C. 34 g. of this product was heated with 12 g. of thionyl an acid obtained from 300 g. of methyl-3-octylaminochloride to some extent on a hot water bath to produce propionate, 200 g. of triethylamine, 344 g. of myristic the corresponding oxychloride. All the resulting oxychloacid chloride, 3 liters of ether and 85 g. of potassium ride was mixed with 23 g. of N-(Z-aminoethyD-l-hyhydroxide with 1.1 equivalent of thionyl chloride.

52 g. of ethyl-p-aminobenzoyl acetate was dissolved in 300 ml. of acetone, 30 g. of triethylamine was added thereto and 103 g. of the oxychloride was added dropwise with stirring at room temperature to deposit triethylamine hydrochloride with some condensate. After the addition, the reaction was continued for 1 hour, 100 ml. of water was added thereto and decanted. Mixed with ligroine in a small amount, crystallized, filtered and recrystallized from acetone. Yield: 20 g., M.P. 70 C.

20 g. of ethyl-p-(3-(N-octylmyristamide) propionamide)-benzoyl acetate was mixed with 5 g. of o-chloroaniline, reacted at 160 C. for V3 hour and, after cooled, crystallized by adding methanol. Recrystallized from ethanol to give 5 g. of a crystal which melted at 130 C.

Example 1 8 g. of the Compound 1 was dissolved in 20 g. of butyl phthalate with heating, the resulting solution was added to a mixed solution of 10 m1. of 5% saponin aqueous solution and 200 ml. of 5% gelatin aqueous solution, made emulsified and added to 500 g. of an emulsion of iodobromide. A film base coated by the resulting emulsion was dried, exposed, developed by the following developing solution, bleached and fixed.

G. 2-amino-5=N,N-diethylaminotoluene hydrochloride 2.0 Sodium sulfite 2.0 Sodium carbonate 20.0 Potassium bromide 2.0 Water to 1 liter.

The cyan image having the absorption maximum at 700 n.m. was obtained. The deposition and aggregation of the coupler could not be observed throughout the process and in the resulting color image and the Heiz value by ASTM was 9.1 at the maximum density. When the Compound 6 was treated in the same manner, the Heiz value reached 16.3 at the maximum destiny.

Example 2 6 g. of the Compound 2 was dissolved in 20 g. of butyl terephthalate and treated as in Example 1 thereby to obtain a magenta image having the absorption maximum at 545 n.m. The deposition and aggregation of the coupler could not be observed throughout the process and in the color image. The Heiz value by ASTM at the maximum density was 10.8, while that of the Compound 7 at the same condition was 50.8.

Example 3 G. N,N-diethyl-p-phenylenediamine hydrochloride 2.0 Sodium sulfite 2.0 Sodium carbonate 20.0 Potassium bromide 2.0

Water to 1 liter.

The Heiz value by ASTM was 3.6 at the maximum density, while that of the Compound 8 was 79.3 at the same condition.

Example 4 10 g. of the Compound 4 was dissolved in a mixed solution of 18 g. of butyl phthalate and 2 g. of o-tolyl phosphate and treated as Example 1 thereby to produce a satisfactory yellow image having the absorption maxi- 6 mum at 442 n.m. The Heiz value by ASTM at the maximum density was 5.8, while that of the Compound 9 at the same condition was 46.8.

Example 5 8 g. of the Compound 5 was dissolved in a mixed solution of 15 g. of butyl phosphate and 5 g. of o-tolyl phosphate, dispersed in the similar manner to that described in Example 1 and processed in the developer described in Example 3 thereby to produce a satisfactory yellow image having the absorption maximum at 430 n.m. The Heiz value by ASTM at the maximum density was 5.7.

What we claim is:

1. A color photographic silver halide emulsion in which a compound represented by the following general structure is incorporated as a coupler:

CH3(CH2) 1C0 NCHaCHaC O-A where A is a coupling component having at least a member selected from the group consisting of ketomethylene group, pyrazolone nucleus, phenol nucleus, and naphthol nucleus, m is an integer from 2 to 7 and n in an integer from 6 to 14 when m is 2, 4, 5, 6 and 7 and n is 14 when m is 3.

2. The emulsion according to claim 1 wherein said coupler is a compound having the following formula:

0 O 2)nCH:

3. The emulsion according to claim 1 wherein said coupler is a compound having the following formula:

4. The emulsion according to claim 1 wherein said coupler is a compound having the following formula:

6. The emulsion according to claim 1 wherein said coupler is a compound having the following formula:

CHa( :)1

References Cited UNITED STATES PATENTS 3,337,344 8/1967 Kimura et a1 96l00 3,135,609 6/1964 Klinger 9610() J. TRAVIS BROWN, Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,418,129 December 24, 1S

Shiro Kimura et a1.

It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

In the heading to the printed specification, line 6, "Fuji Shoshin Film Kabushiki Kaisha" should read Fuji Shashin Film Kabushiki Kaisha Signed and sealed this 2nd day of June 1970.

(SEAL) Attest:

Edward M. Fletcher, Jr.

Attesting Officer Commissioner of Patents WILLIAM E. SCHUYLER, JR.