US3808945A

US3808945A - Light-sensitive silver halide color photographic emulsion

Info

Publication number: US3808945A
Application number: US00236655A
Authority: US
Inventors: I Inoue; T Endo; K Kasai; S Matsuo; S Sato
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 1971-03-29
Filing date: 1972-03-21
Publication date: 1974-05-07
Anticipated expiration: 1991-05-07
Also published as: GB1354437A; DE2214449A1

Abstract

AND X is hydrogen or a group which will split off during the dye forming reaction and will not substantially color the coupler, is incorporated into a photographic material containing a lightsensitive gelatino silver halide photographic emulsion. The resultant material exhibits improved graininess and control of photographic gamma, without exhibiting desensitization.

WHEREIN R is substituted aryl, substituted aralkyl or a saturated or unsaturated aliphatic group having 1-22 carbon atoms; R'' is an aliphatic group having 1-6 carbon atoms; R'''' is COCH3, COOC2H5 or

OR

AND AT LEAST ONE COUPLER OF THE FORMULAS:

An alkoxal-oxy type coupler of the formula:

Description

United States Patent [1 1 Matsuo et al. I

[ LIGHT-SENSITIVE SILVER HALIDE COLOR PHOTOGRAPHIC EMULSION [75] lnventors: Shunii' Matsuo; Shui Sato; Takaya Endo; Keiii Kasai; Izaburo Inoue, all of Tokyo, Japan [73] Assigriee: Konishiroku Photo Industry Co.,

Ltd., Tokyo, Japan 22 Filed: Mar. -21, 1972 21 Appl N6; 236,655

[30] Foreign Application Priority Data 3/1972 lwama et al. 96/100 Primary Examiner-J. Travis Brown Atlorney, Agent, or Firrri-Birman & Bierman 57 ABSTRACT An alkoxal-oxy type coupler of the formula:

0-i J-ii0R' A CONH i [451 May 7,1974

aridat least one coupler of the formulas:

OONH-R 01 NHCO-R W0; 2 e, h

RH G... 2 CONH-R 9 wherein R is sphs tituted aryl, substituted aralkyl or a saturated or unsaturatedaliphatic group having 1-22 carbon atoms; R'- is an aliphatic group having l-6 car bon atoms; R" is COCH COOCJ-l or color the coupler, is incorporated into a photographic material containing a light sensitive gelatino silver halide photographic emulsion. The resultant material ex-,

hibits improved grainine'ss and control of photographic gamma, without exhibiting desensitization.

,4 Claims, 1' Drawing Figure .1 LIGHT-SENSITIVE SILVER HALIDE COLOR PHOTOGRAPHIC EMULSION This invention relates to a light-sensitive color photographic material capable of giving an excellent color photographic imagewhich contains an iodinesubstituted alkoxal-oxy type cyan coupler in combination with one or two of known cyan couplers.

An alkoxal-oxy type cyan coupler has the formula,

where R is asubstitutcd aryl group, a substituted aralkyl group or a saturated or unsaturated aliphatic hydrocarbon radical having one to 22 carbon atoms; R is an aliphatic hydrocarbon radical having one to six carbon atoms; and X is a hydrogen or halogen atom.

The dye-forming reaction mechanism of the alkoxaloxy type cyan coupler has not been clarified yet, though it would be clearly elucidated by. future studies, but is somewhat different from that of a conventional cyan coupler. That is, a cyan coupler having an -OH group in the 4-position and a cyancoupler having an alkoxal-oxy group in such position are greatly different from each other in shape of spectral curve, photosensitivity and graininess, though the two are entirely identical in structure of other portion, and the characteristics of the coupler having an alkoxal-oxy group in the 4- position cannot be anticipated from the coupler having an -OH group. lt may therefore be said that the alkoxaloxy type coupler is differentin kind from the conventional cyan couplers.

According to the present invention, an iodinesubstituted alkoxal-oxy type cyan coupler is used in admixture with other cyan coupler to make it possible tosubstituted coupler, or from a'mixture of said two c'ouplers.

lt was considered that alkoxal-oxy type couplers had However, it' has been found that not only an iodinesubstituted alkoxal-oxy type cyan coupler itself has excellent characteristics but also a mixture of 'said coupler with other cyan coupler results in such remarkable effect that the mixture can display such meritsof alkoxal-oxy type cyan coupler as control of photographic gamma, improvement of graininess, etc., without any desensitization at all.

In case a light-sensitive photographic material is required to be improved .in graininess or controlled in photographic gamma, there has heretofore been used a cyan coupler having an-OH group in the 4-position which contains as substituent an iodine atom or a group capable of being split-off to yield a development inhibitor (Le. a so-called development inhibitor-yielding coupler), as disclosed ,in, for example, US. Pat. No. 3,227,554 or Belgian Pat. No. 737,971. However, an iodine-substituted coupler having an -OH group in the 4-position cannot give such favorable effects as menamples shown later, iodine-substituted cyan couplers of the naphthol or phenol type, which have widely been known hitherto, have no such effect as to lower the photographic gamma, and light-sensitive photographic materials containing said couplers show up such phenomena that they are prevented from desensitization but rather become high in photographic gamma. Accordingly, ordinary iodine-substituted cyan couplers have not been able to improve light-sensitive materials in graininess and to lower them in gamma value, without deteriorating the photos'ensitivities thereof. Further, other substituent than iodine is required to be a group capable of satisfying such conditions that it should be suitable insplit-off rate, should act as a development inhibitor after splitting, and should give no detrimental effect at all, and thus no satisfactory cyan coupler has been obtained yet.

As the result of extensive studies, we have found that a satisfactory cyan coupler. can be obtained by replacing the active point of a cyan coupler with an iodine atom, which is less in problem when the coupler is incorporated into a photographic emulsion, and replacing the hydrogen atom of the -OH group of the coupler with an alkoxal-oxy group. Even when used alone, the iodine-substituted alkoxal-oxy type cyan coupler exhibits excellent characteristics, but it has been found that when the said coupler is used inadmixture with other known cyan coupler, the mixed coupler-displays such effects as control of photographic gamma and improvement of graininess and desensitization which have never been expected hitherto. a

That is, thepresent invention is-concerned with a light-sensitive color photographic material characterized by containing an alkoxal-oxy type coupler of the general formula (I) in combination with one or both of a naphthol type or phenol type colorless coupler of the general formula (II) and a phenol type colored coupler of the general formula (lll).

General formula (I):

oil-Lon General formula (ll):

General formula (III):

GONE-R wherein R is a substituted aryl group, a substituted aralkyl group or a saturated or unsaturated aliphatic hydrocarbon radical having oneto 22 carbon atoms; R is an aliphatichydrocarbon radical having one to six carbon atoms; R is COCH COOC l-l or COUCH:-

and X is a hydrogen atom or an atomic group capable of being split off at the time of dye-forming reaction which does not substantially color the coupler.

Typical examples of the alkoxal-oxy type coupler of the general formula (I) which is used in the present inl5 vention are as follows:

OC-(-OC2H5 GONHCnHM O-CCOC2H u -C0NHC Hrz(n) I- I I l ooNmoHm-o- C5Hn(t)-.

{9 ll .0- -COC4H9(B) C0N H(0Hi)r' Y r r 0( J--o00rHi QONHCuHaKn) 0c--4l-00.H

CONHCmHM ll ll O-C-C-O (5H5 -c ONHCHaOHzNHG OCH-S GraH2r(n) ll ll 0- -o-oclm CONHGisHM v10)1 o omrcwonQmrc ONHCiHm portion is out of the above-mentioned range.

@ CONHCMHM) 0 CONHCMHHUI) Q CONHCnHn i O C ONHC1uHaa(n) coNmcnm-o 0mm) CONH(CHz)4-0 0513110) s on O c oumdm) FOG-(15mm Y QCONH O W 1o OH CONH(CH:):NHCO I I C4H9 C O NHCHzCHzNH C O (51L S (312112501) Examples of the diam-substituted colored coupler of the general formula (III) are as follows:

CzHs

III: l 0H CONHCu Hufi coNmomn-o-Qcmum s nu) JJOCH:

confiwnni-oQomm) rHxK I 00C2H5 l 00cm I l /C2Ha comzcmcm-Qrmcocmomc0N Q O O CzHu 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 in either one, or .if necessary in a mixture, of a high boiling solvent having a boiling point of more than 175 C. such as tricresyl phosphateor dibutyl phthalate and a low boiling solvent such as butyl acetate or butyl propionate. The resulting solution is mixed with an aqueous gelatin solution containing a surface active agent, and the mixed solution is formed intoa dispersion by means of a high speed rotarymixer or a colloid mill. The thus formed dispersion'is added directly to a silver halide photographic emulsion, which is then coated on such a support as glass plate, synthetic resin sheet, film base,

baryta paper or laminated paper, followed by drying to remove a major proportion of the low boiling solvent.

Alternatively the said dispersion is set, finely cut to noodless and freed fromthe low boiling solvent by water-was'hing or the like procedure, and the residue is added to a light-sensitive photographic emulsion, which is then coated on the above-mentioned support,

followed by drying. in the above manner, a lightsensitive color photographic material of the present in-, sm onsan l attained- The amount of the couplers to be added is ordinarily within the range from 5 to mole percent based on the amount of the silver halide used. However, equiva-' lent effects can, of course, be obtained even if the amount of the couplers is out of said range. i The light-sensitive photographic material of the presvent invention may be" developed according to any procedure for the development of ordinary light-sensitive color photographic materials, and no particular considi s'a r l lal .Ea m That is, as the color developing agent, there may be used any of such aromatic primary amino compounds as set forth below. i 'l. Diethyl-p-phenylenediamine hydrochloride 2. Monomethyl-p-phenylenediamine hydrochloride 3. Dimethyl-p-phenylenediamine hydrochloride 5 4. 2-Amino-5-diethylaminotoluene hydrochloride 5.-2-Amino-5-(N-ethyl-N dodecylamino)-toluene The developer solution may contain a'sulfite, carbonate, bisulfite, bromide or iodide of'an alkali metal. The I photographic emulsion used in the present invention may have been chemically sensitized or may have been optically sensitizedby means of a carbocyanine, merocyanine or the like dye, and may have been incorporated with ordinary photographic additives such as, for

6. N-EthylfN-li-methanesulfonamidoethyl-3-rnethyl-4- H N-MethylN43-rhethanesulfonamidoethyl-4- u -veloped at 20 C. for 10 minutes with ,LlllO s w p si is a. I

example, antifoggant, stabilizer, anti stain agent, physical property-improvinghigh molecular additive, hardener, coating aid, etc. When an ultraviolet absorber is incorporated into a light sensitive color photographic material containing the couplers used in the present invention, a color image obtained from the photographic;

material can further be enhanced in durability. Furthermore, the color developer solution may contain, in

addition to the aforesaid developing agent, such a de-v velopment controller as citrazinic acid orthe like.

Anhydrous sodium sulfitc 2.0 g. Benzyl alcohol 3.8 g. Sodium carbonate (monohydrute) 5.0 g. Potassium bromide l.0 g. Caustic soda 0.55 g. )Yater to make I 000 ml.

The accompanying drawing shows the spectral curves of the light-sensitive color photographic materials of the present invention which are described in Ex- 392. sbwnl The present invention ishiiisiriciiiiid'rfilr"il'iif below with reference to examples, but it is needless to say that the scope of the invention is not limited to these.

EXAMPl E l PREPARATION OF SAMPLES l Sample 1: y

2.0 Grams of the exemplified coupler "-1 was dissolved at 60 C. in a mixed solvent comprising 2.0 ml.

of dibutyl phthalate and 3 .0 ml. of butyl acetate. The

Sample 3: r

'A mixture of 1.0g. of the exemplified. coupler 1-! and 1.0g. of the exemplified coupler Il-l was treated in the same. mapper as in the case of the ,sample l Sample 4:

A mixture of 1.6g. of the exemplified coupler l-Z and 0.4g. of the exemplified coupler lIl-2was treated in the same manner as in the case of the sample 1.

Sample 5 A mixture of 1.2g. of the exemplified coupler l-l,

0.6g. of the exemplified coupler [1-3 and 0.4g. of the exemplified coupler III-2 was dissolved in-a mixed solvent comprising 2.5 ml. of dibutyl phthalate and 5.0 ml. of butyl acetate, and the resulting'solution was treated in the -.same manner as in the caseof the sample l.

. The above-mentioned samples were individually/ex posed according to an ordinary procedure and-then dea developer of the N-Ethyl-N-fi-methunesull'onumidoethyl 3-methyl-4- 5.0 g. uminounillnesultate Subsequently, the developed samples .were subjected to ordinary stop-fixing treatment, 'washed' with waterfor X0 to 15 minutes, and then treated for 5 minutes Thereafter, the samples were washed with .water for 5 minutes and then dried. Photographic properties of he t u rss sdsaup ssw as so. rth l! Table treated in the same manner as in the case of the sample pler I-3 and 0.4 g. pf the exemplified coupler Ill-2 were Table 1 Relative Gamma D-max Grainin- Sample speed ess l Exemplified 100 0.98 2.05 Relativecoupler ll-l ly fine 2 Exemplified 86 0.79 [.87 Fine coupler l-l 3 Exemplified coupler l-l 93 0.92 2.10 Fine (111 l. 4 ifisd A coupler l-Z 90 0.91 1.74 Fine do. ill-2 5 Exemplified coupler l-l do. "-3 96 0.94 l.6l Fine do. Ill-2 Table 2 Relative Gamma D-max Grainin- Sample speed (-y) ess 1 Ex empli'fied 100 1.13 2.32 I Relativecoupler 6 I ly fine 2 Exemplified coupler l-3 95 0.98 2.20 Fine do. "-6 3 Exemplified coupler l-3 do. "-6 92 0.94 2.14 Fine do. Ill-2 Spectral curves of the samples 1,3 and 5 were as 0 0 shown in the accompanying drawing, in which the dot- EJL I ted line solid line and chained line show the spectral curves of the samples 1, 3 and 5, re-

spectively.

A high speed emulsion after completion of chemical ripening was subjected to optical sensitization by addi tion of a red-sensitive sensitizing dye 3,3'-diethyl-5,5'- dichloro-Q-ethylthiacarbocyanine bromide. This emulsion was divided into three portions (each 100 ml. in amountlto prepare samples 1, 2 and 3. On the other hand, 2.0 gi o f the exemplified couplerll-6, a mixture of 1.0 g. of the exemplified coupler [-3 and l .0 g. of the exemplified coupler 11-6, and a mixture of 1.0 g. of the exemplified coupler 11-6, 0.8 g. of the exemplified cou- '40 sa d s t r slatllk being 1 coma-a or.

individually dissolved'in a mixed solvent comprising 20 ml. of dibutyl phthalate and 6.0 ml. of butyl acetate, X and then dispersed in the same manner as in Example m MM 1 to prepare coupler dispersions (a), (b) and icl e- I spectively. The dispersion (a) was added to the sample 1, the dispersion (b) to the sample 2, and the dispersion (c) to the sample 3. Thereafter,'the samples 1, 2 and 3 were treated in the same manner as in Example l to obtain the results as set forth in Table 2. E

As is clear from Table 2, the samples according to the present invention are favorable in control of gamma and in graininess, and are excellent as 'lightsensitive color photographic materials.

What we claim is:

and said general formula (III) being l. A light-sensitive gelatino silver'halide color photographic emulsion whichcontains an alkoxal-oxy type coupler of the general formula (1) in combination with one or both of anaphthol or phenol type colorless coupler of the general formula (ii) and a phenol type colored coupler of the general formula (III) said general 'form ulai l) being carbon atoms which radical may be substitutedwith an W 15 I 16 aryloxy or carbonamido group; R is an aliphatic hydrocolorless compler of the general formula (II) is a comcarbon radical having one to six carbon atoms; R" is pound of the following structural formula Q CHQ. TCQQCZH5 or Hll v OH and X is a hydrogen atom or an'aEGTnT'glBiE capable 5 CONH' R of being split off at the time of dye-forming. reaction 4 which group is selected from a chlorine atom, a brole? .29%". is

wherein R is arTalkyl group. 10" 4. A light-sensitive gelatino silver halide color photographic emulsion as claimed in claim 1, wherein said g colored coupler of the general formula (Ill) is a com- I l I (E Q pound of the following structure formula 000- N ND \Ny v 03 s-0H I i ooNacnmvm) HOOC/ \COOH, solanacoomon and I Y I g r I t @m-H@ ooomQ I c211 i CONH(CH:)aO CsHn( 2. A light-sensitive gelatino silver halide color photov a nU) graphic emulsion as claimed .in claim l, wherein said alkoxal-oxy type coupler of the general formula (I) is a compound of the following structural'formula v v i .,.,e. nuts g w 4 I 1 v 0 0 v O---OR wherein R is an alkyl group and n is an integer of not 43000,}: Pa. l ss than 12. v v g Q A ght'sensitive latino silver halide colorphoto 4 raphic emulsion as claimed in claim 1 wilqgin said. a

Claims

2. A light-sensitive gelatino silver halide color photographic emulsion as claimed in claim 1, wherein said alkoxal-oxy type coupler of the general formula (I) is a compound of the following structural formula
3. A light-sensitive gelatino silver halide color photographic emulsion as claimed in claim 1, wherein said colorless compler of the general formula (II) is a compound of the following structural formula
4. A light-sensitive gelatino silver halide color photographic emulsion as claimed in claim 1, wherein said colored coupler of the general formula (III) is a compound of the following structure formula