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Publication numberUS3737318 A
Publication typeGrant
Publication dateJun 5, 1973
Filing dateMay 13, 1971
Priority dateMay 14, 1970
Also published asDE2123447A1, DE2123447B2
Publication numberUS 3737318 A, US 3737318A, US-A-3737318, US3737318 A, US3737318A
InventorsEndo T, Hanzawa T, Inoue I
Original AssigneeKonishiroku Photo Ind
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Light-sensitive color photographic material
US 3737318 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent US. Cl. 96-400 11 Claims ABSTRACT OF THE DISCLOSURE A light-sensitive silver halide color photographic material containing as a coupler a compound of the general formula,

N H CH3- wherein R is a hydrogen atom or a lower alkyl group; R is an aliphatic hydrocarbon residue having 8 to '18 carbon atoms; 11 is zero or 1; and m is zero or 1.

This invention relates to a light-sensitive color photographic material. More particularly, the invention is concerned with a color photographic material containing a blue image-forming novel coupler belonging to the socalled protect type coupler, i.e. a Water-insoluble or difficultly water-soluble coupler to be used by dissolving the same in a diflicultly water-miscible high boiling solvent and dispersing the resulting solution in a photographic emulsion. The novel coupler is represented by the general formula,

wherein R is a hydrogen atom or a lower alkyl group, R is an aliphatic hydrocarbon residue having 8 to 18 carbon atoms, m is zero or 1, and n is zero or 1. 7

Although many compounds have heretoforebeen proposed as protect type couplers, they have various draw-. backs, and those which can be prepared at low cost and with high purity have scarcely been known. For example, the coupler of the formula,

01- NHCOCH--O tCsHn $.11. CH t 5 1! COCH-O- o1 NHCOCHzO 3,737,318 Patented June 5, 1973 it is easily soluble in a high boiling solvent such as dibutyl phthalate, tricresyl phosphate or the like, so that the amount of the solvent for the coupler can be decreased to make it possible to obtain a high concentration coupler dispersion. Further, the coupler is low in melting point and hence is diflicultly crystallizable in an emulsion or in a film formed by coating and drying. Due to such characteristics as mentioned above, the coupler of the present invention is quite useful as a protect type coupler, and has greatly overcome the drawbacks of known couplers. Accordingly, the light-sesitive color photographic material according to the present invention, which has been incorporated with the said coupler, is excellent in spectral absorption characteristic and can give a high densitv color 15 image excellent in transparency.

The coupler used in the present invention is synthesized, for example, in the following manner:

A long chain alkyl bromide and catechol are condensed with each other in dimethylformamide in the presence of potassium bicarbonate to form a catechol monoalkyl ether, which is then condensed with a halogenated fatty acid to obtain a long chain alkoxyphenoxy fatty acid. This acid is treated with phosphorus pentachloride to form an acid chloride, which is then condensed with a phenol derivative having an amino group in the o-position to synthesize the desired coupler.

Typical examples of the couplers represented by the general formula are set forth below, but couplers usable in the present invention are not limited only to these.

01 NHE0 momma-G 1 L NH-COCHO O C aHu Z-[a- (2-octyloxyphenoxy)butylamide]-4,6-dichloro-5- methylphenol O C ioHzi 1 2- (Z-decyloxyphenoxy acetamide -4, 6-dichloro-5- methylphenol 3. OH 0 01211 5 01 NHCO CHzOQ 01 2-(2-dodecyloxy acetamide)-4,6-dichloro-5- methylphenol OH 012B 01 NHCOCH-O r CH3 2 2- [oc- (Z-dodecyloxyphenoxy) butylamide]-4,6-dichloro--.

methylphenol OH O C 4Hzn 01* NBC 0 (DH-O CH3 CH3 2- [u- (Z-tetradecyloxyphenoxy) propion amide] -4,6- dichloro-S-methylphenol NHCOCHzO 2- [a- Z-hexadecyloxyphenoxy) butylamide] -4,

dichloro-S-methylphenol OH OCmHu C1 NHCOCHzO 2- (2-octade cyloxyphenoxy acetamide) -4,6- dichloro-5 -methylphenol on 01 NHC OQNHGOCH-OQ CH3 I 2- [4-( a-dodecyloxyphenoxy) butyl amide] benzamide-4, 6-

dichloro-S-methylphenol 01 NHCO- O CnHzs CH3 NBC 0 CHzO 2-[3-(2-dodecyloxyphenoxy acetamide)benzamide] -4,6- dichloro-S-methylphenol NHCOCH O-QNHCOZHOQ 4 Synthesis example (a) A mixture comprising 110 g. of catechol, 500 ml. of dimethylformamide, 140 g. of potassium carbonate and 280 g. of dodecyl bromide was stirred at 110 to 120 C. for 3 hours. Subsequently, the mixture was poured into water, and the oil layer was extracted with ether, washed with water and dried with Glaubers salt. Thereafter, the ether was removed by distillation, and then the residue was subjected to distillation to obtain a fraction of catechol monododecyl ether, B.P. 203-205 C./ 4 mm. Hg, yield In the same manner as above, there were obtained catechol monooctyl ether, B.P. l183 C./4 mm. Hg; catechol decyl ether, B.P. 192-195 C./4 mm. Hg; catechol tetradecyl ether, B.P. 220-225 C./4 mm. Hg; catechol hexadecyl ether, B.P. 225228 C./4 mm. Hg; and catechol octadecyl ether, B.P. 230-235" C./3 mm. Hg.

(b) 86.5 grams (0.3 mole) of the thus obtained catechol monododecyl ether was added to a solution of 13.8 g. of metallic sodium in 300 ml. of alcohol, and the resulting mixture was boiled for 30 minutes. Thereafter, the mixture was charged with 50.5 g. (0.3 mole) of a-bromobutyric acid, stirred with boiling for 3 hours, poured into ice water and then acidified with hydrochloric acid to deposit a precipitate. The precipitate was recovered by filtration and then recrystallized from n-hexane to obtain a-(2-dodecyloxyphenoxy) butyric acid, M.P. 74-76 C.,

yield 75%.

In the same manner as above, there were obtained various long chain alkoxyphenoxy fatty acids, i.e. 2-dodecycloxyphenoxy acetic acid (M.P. 6870 C.) from catechol monododecyl ether and monochloroacetic acid; Z-decycloxyphenoxy acetic-acid (M.P. 75-78 C.) from catechol monodecyl ether and monochloroacetic acid; a-(2-octyloxyphenoxy) butyric acid (M.P. 78-80 C.) from catechol monooctyl ether and a-bromobutyric acid; u-(Z-tetradecyloxyphenoxy) propionic acid, M.P. 79-81 C.) from catechol monotetradecyl ether and a-bromopropionic acid; m-(Z-hexadecyloxyphenoxy) butyric acid (M.P. 88 C.) from catechol monohexadecyl ether and a-bromobutyric acid; and 2-octadecyloxyphenoxy acetic acid (M.P. 98 C.) from catechol monooctadecyl ether and monochloroacetic acid.

(c) The thus obtained long chain alkoxyphenoxy fatty acid was treated with phosphorus p'entachloride to form' an acid chloride. For example, a suspension of 36.4 g. of Z-dodecyloxyphenoxy acetic acid in ml. of chloroform was charged with 23 g. of phosphorus pentachloride, and the resulting mixture was allowed to stand for 30 minutes and then heated for 30 minutes in a water bath at 60 C. Thereafter, the formed phosphorus oxychloride and chloroform were removed by distillation under reduced pressure, and the residual chloride was used in the subsequent acylation step.

(d) 40.0 grams of the thus obtained chloride was added to a mixture comprising 22.9 g. of 2-amino-4,6-dichloro- S-methylphenol hydrochloride, 550 ml. of acetone and 25.0 g. of diethyl aniline, and the resulting mixture was stirred for 1 hour, boiled for an additional 1 hour and then filtered. Subsequently, the filtrate was concentrated, and the concentrate was poured into a mixed liquid of concentrated hydrochloric acid and water, whereby a solid mass separated from the oil. The thus formed solid was recovered by filtration, washed with water, dried and then recrystallized from hexane to obtain 36.0 g. (64.5%) of a white powder having a melting point of 73 to 75 C. This powder was the exemplified coupler (3) of the present invention.

In the same manner as above, the exemplified couplers and could be synthesized by the condensation of acid chlorides hav ing different alkyl chains.

Tables 1 and 2 show the fact that the couplers used in the present invention have a low melting point and have excellent solubility in a high boiling solvent as compared with known couplers.

In Table 2, the comparison in solubility in a high boiling solventwas carried out by measuring the amount of dibutyl phthalate necessary to dissolve 1 :gl of coupler at 60 C.

In order to substantiate the fact that thecouplers of the present invention are excellent in durability, particularly heat resistance, of the resulting color images as compared with known couplers, the exemplified coupler (4) and know couplers were individually treated in the same manner as in Example 2 mentioned later, and the resulting color images were subjected to heat resistance test (at 77 C. for 2 days) and light resistance test (irradiation with an arc-lamp for 32 hours) to obtain such results as set forth in Table 3, in which the heat and light resistance values are residual color ratios at a density of 1.0.

TABLE 1.OOMPARISON IN MELTING POINT BETWEEN THE PRESENT COMPOUNDS AND KNOWN COUPLERS SIMILAR IN STRUCTURE THERETO Coupler Structural formula M.P. C.)

Exemplified OH 0 0121325 73-75 coupler (3).

C1- NH0 0 01120-- Known coupler. I)H 158-160 01- NBC 0 CHgO- tCsHll CH tCaHu Exemplified o C12H2s 69-71 coupler (4). i- I NBC 0 crew-Q Known coupler. 123-124 aHu TABLE 2.COMPARISON IN SOLUBILITY I Amount of dibutyl phthalate Coupler Structural formula (ml Elgmpllfied coupler (XE O CizHzs 1. 5

01- NH0 0 CH0 Known coupler.. OH 3. 0

Cl- NH0 0 CHO- tCsHn TABLE 3.COMPARISON IN HEAT AND LIGHT RESISTANCE wists Heat Light... s resistresist- Coupler Structural formula ance ance Known coupler--- H 83 97 Cl NHCOCH-O tCaHn 32115 CH t sHu Cl j Y.

Do 11 7d 921 o1- NHCOCH-OQ Exemplified 0 0121125 coupler (4).

As is clear from Tables 1, 2 and 3, it is understood that the couplers used in the present invention are not only low in melting point but also excellent in solubility in high boiling solvents and particularly high in durability of resulting color images as compared with known couplers, and hence are extremely useful as protect type couplers.

In order to incorporate the couplers used in the present invention into a light-sensitive color photographic material, there may be adopted any of the known procedures. For example, the couplers are dissolved either singly or in combination of 2 or more in a high boiling solvent (B.P. 175 C. or more) such as tricrcsyl phosphate or dibutyl phthalate, or a low boiling solvent such as butyl acetate or butyl propionate, or a mixture of said solvents. This solution is mixed with an aqueous gelatin solutioucontaining a surface active agent and then emulsified by means of a high speed rotary mixer or a colloid mill. Subsequently, the emulsified liquid is added directly to a silver halide photographic emulsion, which is then coated on a support such as a glass plate, synthetic resin sheet, film ing aids, etc. Still further, the emulsion may contain a known carbocyanine or merocyanine dye as an optical sensitizer therefor.

'The thus obtained light-sensitive color photographic material is exposed to radioactive rays such as a-rays or S-rays, visible rays or infrared rays, developed with a 5 developer containing a p-phenylenediamine type developing agents as an active ingredient, and then bleached, desilvered and fixed to obtain a-high density color. image which'is excellent in spectral absorption characteristicsfand durability andl iglr in transparency.

40 A color photographic material using the coupler of the present inventionrnay be incorporated with an UV- absorber of the benzophenorie t'ype (e.-g. 2-hydroxy-4- dodecyloxybenzophenone) or the triazole type [c.g. 2(2'- hydroxy-3,5'-di-tcrt-butylphenyl) benzotriazole], whereby the resulting image can further be increased in durabilityl base, baryta paper or laminated paper, followed by dryethyl N B methanesulfonamidoethyl y ing, to prepare a light-sensitive color photographiiunaie-w rial. Alternatively, the above-mentioned emulsified liquid is once set, finely cut, freed from the low boiling solvent by water-washing or the like means and added to a photo- .ra a acaail heaelinthyl.eliehytlmxr hxl.aparhenyla enediamine, N ethyl N hydroxyethyl 2 methyl-pphenylenediamine and N,N diethyl 2 methyl-p-phenylenediamine. Further, the developer may contain a developgraphic emulsion, which is then coated on a support such mam-Controlling agent, -8- citralinic acid, in addition to as mentioned above, followed by drying, to prepare a lightsensitive color photographic material. T" The above-mentioned procedures are illustrative and are not limitative. i

to the photographic emulsion is preferably in the range of 10 to g. per mole of silver halide but may be varied as occasion demands without being limited to said range. Further, the coupler may be incorporated into 2 or more different emulsion layers of a multi-layered color photo- 65 graphic material.

The photographic emulsion used in the present invention may be prepared by use of various silver halides such as silver chloride, silver iodobromide or silver chlorobromide,

the above-mentioned active ingredient! The present invention is illustrated *in further rletail EXAMPLE 1 10 grams"of the exemplified coupler (3) was added to a mixed solution comprising 10 ml. of tricresyl phosphate and 30 ml. of butyl acetate, and the resulting mix ture was heated to 50 C.,' whereby the coupler was completely dissolved. This solution was mixed with 5' ml. of a 10% aqueous solution of Alkanol B and 800 ml.

and may contain a chemical sensitizer, 61g. sulfur sensi- 70,1 q c ussolutio g and the resulting tizer, a natural sensitizer present in gelatin, a reducing sensitizer or a noble metal salt. Further, the emulsion may have been incorporated with any of ordinary photographic additives such as, for example, anti-foggants, stabilizers,

mixture'was' subjected to a -;colloid mill to form a dispersionTIlhis dispersion was added-M500 g. of a gelatin silver 'iodobromide emulsion, which was then coated on a film base and dried to obtain a photograpl:r ic rna;

anti-irradiation agents, anti-stain agents, hardener sfcoafi 7 t'erial having a stable film coating. This photographic ma- 7 terial was exposed and then developed at 21 C. for 12 minutes with a developer of the following composition:

G. Metol 3.0 Anhydrous sodium sulfite 50.0 Hydroquinone 6.0 Anhydrous sodium carbonate 40.0 Potassium bromide 3.5 Potassium rhodanide 2.0

Water to make 1,000 ml.

Thereafter, the material was subjected to ordinary stopping, film-hardening and water-washing treatments, and then subjected to second exposure by use of a white Water to make 1,000 ml.

Thereafter, the thus treated material was washed with water for minutes, dipped in a stabilization bath for 2 minutes and then dried to obtain a cyan color image 10 which had an absorption maximum at 670 m and was excellent in resistance to light and moisture.

What we claim is:

1. A light-sensitive silver halide color photographic material characterized by containing as a coupler a comlight. Subsequently, the thus treated material was depound f h general f la,

JR Rt veloped at 21 C. for 13 minutes with a developer of the following composition:

N,N-diethyl-2-methyl-p-phenylenediamine 3.0 Anhydrous sodium sulfite 4.0 Sodium carbonate (monohydrate) .L 20.0 Potassium bromide 2.0

Water to make 1,000 ml.

A mixture comprising 10 g. of the exemplified coupler (4) and ml. of dibutyl phthalate was heated to 50 C. to form a solution. This solution was mixed with 5 ml. of a 10% aqueous Alkanol B solution and 200 ml. of a 5% aqueous gelatin solution, and the resulting mixture was subjected several times to a colloid mill to form a dispersion. This dispersion was added to 500 g. of a gelatin silver chlorobromide emulsion, which was then coated on a baryta paper and dried to prepare a light-sensitive material.

The thus prepared material was exposed and then developed at C. for 10 minutes with a developer of the following composition:

N-ethyl-N-B methanesulfonamidoethyl-3-methyl- N ethyl N p-methanesulfonamidoethyl-3-methyl- Water to make 1,000 mil.

The developed material was then dipped for 2 to 4 minutes in a stopping-fixing bath of the following composition:

Ammonium thiosulfate g 120 Potassium metabisulfite g 20 Glacial acetic acid cc 10 Water to make 1,000 mil.

Subsequently, the material was washed with water for 5 minutes and then bleached at 25 C. for 3 minutes in a bath of the following composition:

wherein R is a hydrogen atom or a lower alkyl group; R is an aliphatic hydrocarbon residue having 8 to 18 carbon atoms; n is zero or 1; and m is zero or 1.

2. A light sensitive silver halide color photographic material as claimed in claim 1 wherein the coupler is 2-[a-(2 octyloxyphenoxy)butylamide]-4,6 dichloro-S- 0 methylphenol.

3. A light sensitive silver halide color photographic material as claimed in claim 1 wherein the coupler is 2-(2-decyloxyphenoxy acetamide)-4,6 dichloro-S-methylphenol.

4. A light sensitive silver halide color photographic material as claimed in claim 1 wherein the coupler is 2-(2-dodecyloxy acetamide) 4,6 dichloro-S-methylphenol.

5. A light sensitive silver halide color photographic material as claimed in claim 1 wherein the coupler is 2-[a-(2-dodecyloxyphenoxy)butylamide] 4,6 dichloro- 5-methylphenol.

6. A light sensitive silver halide color photographic material as claimed in claim 1 wherein the coupler is 2-[01-(2 tetradecyloxyphenoxy)propionamide] 4,6-dichloro-5-methylphenol.

2-[3-(2 dodecyloxyphenoxy acetamide)benzamide]-4,

6-dichloro-S-methylphenol.

11. A light sensitive silver halide color photographic material as claimed in claim 1 wherein the coupler is 2-[4-(a'. 2 dodecyloxyphenoxy butylamide)phenoxy acetamide]-4,6-dichloro-S-methylphenol.

References Cited UNITED STATES PATENTS 2,698,794 1/1955 Godowsky 96-400 2,908,573 10/ 1959 Bush et al. 96-100 3,652,286 3/1972 Credner et al 96-100 J. TRAVIS BROWN, Primary Examiner US. Cl. X.R. 260-559

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3891445 *Jun 18, 1974Jun 24, 1975Fuji Photo Film Co LtdColor photographic light-sensitive materials
US6706664Apr 27, 2000Mar 16, 2004Ube Industries, Ltd.Benzoxazole compounds, process for the preparation thereof and herbicides
WO2000066569A1 *Apr 27, 2000Nov 9, 2000Takehiko AsaharaBenzoxazole compounds, process for the preparation thereof and herbicides
Classifications
U.S. Classification430/553, 564/175, 564/142, 564/158
International ClassificationC09B53/00, G03C7/34
Cooperative ClassificationG03C7/346
European ClassificationG03C7/34P