DE2221111A1 - Light sensitive photographic recording material - Google Patents

Description

48 454

Applicant: Konishiroku Photo Industry Co., Ltd. ■ '■■ - ■ 1-10, 3-Chorae, Hihonbadi-Kurormaohi, Chuor? Ku,

Tokyo, Japan

Sankyo Company Limited,

1-6, 3-Chome, Nihonbashi-Hon-cho, Chuo-ku,

Tokyo, Japan

Light sensitive photographic recording material

The present invention relates to a photosensitive Photographic recording material with at least one silver halide emulsion layer, the new antifoggant contains.

The mechanical and rapid treatment of photosensitive photographic recording materials has become increasingly important, and it has become common practice to treat photographic recording materials under conditions as severe as previously thought to be impossible. Therefore, when common photographic recording materials are treated as they are, various unexpected difficulties arise. For example, when a photographic material is processed automatically and quickly using an automatic developing machine, fogging is apt to be caused by the decomposition of the developer, which is different from a conventional developer, or the high temperature used in the development.

209851/1019

ORfGfNAL! MSPECTED

thus often the image obtained in terms of its quality is adversely affected. This tendency becomes more pronounced when the photographic recording material is more sensitive or the development is carried out more quickly. Attempts have been made to produce this fog Prevent use of common antifoggants. However, the amount of usual fogging agents required is in this case 4 to 10 times the amount under normal Circumstances required v / ird. This results in a noticeable desensitization. Therefore the use of conventional anti-fogging agents is not a practical solution ", ■ and the actual state is characterized in that. there is practically no antifoggant that would be capable of to prevent the described veil.

The object of the present invention is essentially to be found based on a light-sensitive photographic recording material with at least one silver halide emulsion layer to find the one mentioned above. Does not fog and has excellent photographic properties possesses even if it is treated under severe conditions.

After extensive research, it has now surprisingly been found that the above problem can be achieved in this way can that in at least one of the layers of the recording material, i.e. at least one of the layers applied to the support Layers such as the subbing layer, an intermediate layer, emulsion layer, protective layer, etc. one Compound of the general formula I mentioned below is incorporated.

The present invention accordingly provides a photosensitive Photographic recording material with at least one silver halide emulsion layer, which is characterized by is that there is a compound of the general formula in at least one layer

209851/1019

ORIGlNAi.

I.

R ₂

wherein X is P or N, R ₁ , R ₂ , R-, and R _{/ +} each represent an alkyl, aryl or aralkyl group, where at least one of the radicals R ^, R £, R- * and R ^ represents an aryl or aralkyl group with an electron-withdrawing ¹ substituent, and X ~~ represents an acid anion. .

Compounds of the above general formula I can be prepared according to the Processes can be prepared in the following preparation examples are described.

Production example 1,

Preparation of p-nitrophenyl-p-toluyl-phenylphosphonium iodide (for example named compound no. 1):

13.8 g of p-nitroaniline were dissolved at elevated temperature in a solution of 30 ml of concentrated hydrochloric acid (35 %) and 20 ml of v / water. The solution was poured into 170 g of ice. A solution of 6.91 g of sodium nitrite in 20 ml of water was then added to this solution. The solution mixture was then left to react for 30 minutes at 0-5 ° C. with stirring, a p-nitroaniline diazonium salt solution being formed. A solution of 30 g of sodium acetate in 50 ml of water was added to this solution and then a solution of 29.0 g of di-p-toluylphenylphosphine in 40 ml of ethyl acetate. The mixed solution was allowed to ^{react at 25 °} C. for 10 hours. After completion of the reaction, the aqueous _β λ

209851/1019

Layer separated with an excess of hydriodic acid added and then extracted with chloroform. The chloroform layer was concentrated to yield 16.7 g of the desired product were obtained. The elemental analysis showed the in. ■ Values given in Table -1.

Production example 2

Preparation of p-nitrobenzyl triphenylphosphonium bromide (for example named compound no.3):

A Geraisch of 22 g of triphenylphosphine and 16.6 'g p-nitrobenzyl bromide was dissolved in 200 ml of xylene, ^1, and the resulting solution was boiled for 26 hours under reflux, whereby a precipitate separated. This precipitate was collected by filtration and then washed with 20 ml of xylene to give 35.6 g of the desired end product. The elemental analysis gave the values given in Table 1.

Other compounds can also be prepared according to the preparation methods outlined above. Typical examples for compounds produced in this way are compiled in Table 1 below. Typical electron attractive Substituents in the compounds of the formula I are nitro, cyano, carbonyl, carboxyl, sulfonyl and quaternary amino groups and halogen atoms.

209851 / T01S

For example, mentioned

JLAJj. jj.iljj! » I.

Formula

Elementary analysis

calculated

(1)

C 57.90 C 58.10

H 4.30 H 4.25

N 2.60 N 2.58

I 23.53 I 23.60

P 5.74 P 5.91

(2)

he

C 75.08 C 75.01

H 4.09 H 4.30

N 3.50 N 3.50

Cl 8.87 Cl 8.92

P 7.75 P 7.45

(3)

C 62.77 C 62.50

H 4.43 H 4.40

Br "N 2.93 N 2.78

Br 16.71 Br 17 * 01

P 6.48 P 6.52

(4)

C 69.21 C 69.18

H 4.88 H 4.78

Cl "N 3.23 N 3.10

Cl 8.17 Cl 8.01

P 7.14 P 7.18

(5)

C 37.46 C 37.44

H 4.71 H 4.81

N 7.28 N 8.00

Cl 9.22 Cl 9.36

P 8.05 P 8.15

209851/1019

Cl

C 55.55 C 55.91

II 8.16 H 8.21

Br ~ N 3.24 N 5.20

Br 18.48 Br 18.35

P 7.16 P 7.01

C 67.17 G 67.85

H 4.08 H 4.00

N 6.30 N 5.99

Cl 7.97 Cl 7.85

P 6.96 P 7.01

Cl

C 71.55 C 71.72

H 4.75 H 4.91

N 6.96 N 6.75

Cl 8.80 Cl 8.75

Cl "

C 78.67 C 78.91

H 5.33 H 5.24

N 7.06 N 7.05

Cl 8.93 Cl 8.52

Br

C 55.57 C 55.68

H 4.43 H 4.61

N 3.24 N 3.20

Br 18.49 Br 18.51

P 7.17 P 7.07

COOC ₂ H ₅

C 57.13 C 57.41

H 5.19 H 5.30

I 25.15 I 24.75

P 6.14 P 6.34

209851/1019

BP

Cl "

C 69.70 C 70.31

H 6.27 H 6.01

Cl "Ii 2.90 N 3.20

Cl 14.70 Cl 14.51

P 6.42 P 6.21

C 59.54 C 59.76

H 4.40 H 4.32

S 6.36 S 6.70

F 15.07 F 15.21

P 6.14 P 6.01

C 74.90 C 75.02

H 5.32 H 5.10

Cl 8.27 Cl 8.05

P 7.43 P 7.56

(O), ⁵ *

Cl "

C 70.42 C 70.67

H 4.68 H 4.73

Cl 17.33 Cl 17.12

P 7.57 P 7.48

209851/1019

The above compounds according to the present invention are excellent in anti-fogging effect Compare with the conventional anti-fogging agents and successfully prevent the fogging that is otherwise under hard .Conditions, as stated above. Bs It is believed that this excellent effect is attributable to the fact that the compounds of the above general Formula I, which are used according to the invention, in the molecule an aryl or aralkyl group with an electron-withdrawing group Have substituents. (Of course, the aryl or aralkyl groups mentioned can have other substituents) This is confirmed by the fact that a compound that has a chemical structure similar to that of a compound according to the invention, but contains an aryl or aralkyl group without 'electron-withdrawing substituents, although effective can prevent the formation of normal fog in a photographic recording material, but substantially shows no effect on fog generated when the photographic material was treated under severe conditions. This follows from the following example 1.

For incorporation into a layer of a photosensitive, silver halide-containing photographic recording material, the compounds of the general formula I can be dissolved in water or in a water-miscible organic solvent such as methanol, ethanol etc. and then incorporated into a suitable layer. The amount used varies in the above case depending on the type of silver halide, the type of layer into which the compound is incorporated, the type of compound used, etc. In general, however, it is advantageous if the compounds according to the invention in an emulsion layer can be incorporated in an amount in the range from 10 to 10 ^J mol per KoI SiI-Berhalogerl. Those worked into a subbing layer, intermediate layer, protective layer, etc. *

209851/1018

Mole

Amounts are advantageously in the range from 10 to 10 / per m based on the photographic recording material. However, the amounts are not always limited to these ranges ..and can be more suitable depending on the desired application Way to be selected.

The silver halide emulsions used in the photographic recording materials in which the compounds may be incorporated according to the invention, any Be emulsions of silver halides such as silver iodobromide, silver chloride bromide, silver chloride iodobromide, Silver bromide and silver chloride »The-mentioned emulsions can be according to the state of the art in the field of photography any inhibitors, stabilizers, sensitisers containing dyes, couplers, sensitizers, hardeners and other photographic additives. Even if, if the connections according to the. Invention present together with such various additives, they result in the described Effect without causing any adverse interactions.

In the light-sensitive, silver halide-containing photographic Recording materials thus obtained are not only prevented from normal fogging, but also it is also effective to prevent fogging under severe conditions which has hitherto been achieved by using conventional ones Antifoggants could not be prevented.

Ausserdera have the property of the compounds used according to the invention is that it effectively prevent the increase in fogging, which is the by-products of a polyester-carrier- or catalyst residues attributed to or dergleicher, when a polyester resin has been used as a carrier for the photographic Aufzeichnungsiaaterial Istv - ■ · ■ ^: "■ ■ ·". ".-. · ---. ■■ ■■■ '. ·. ·. ■: - · ..-. ·'

- 10 -

The invention is further developed with the aid of the following examples explained. However, the invention is not intended to be limited to these examples.

example 1

A silver iodobromide emulsion containing 1.5 KoI ^Γ ,!> Silver iodide was subjected to the usual second ripening process and then 4-hydroxy-δ-methyl-1,3,3a, 7-tetrazaindene was added. The emulsion was then divided into several equal portions, to which the compounds listed in Table 2 were then added in each case. In addition, the emulsions were each made with formalin and saponin. added, applied to a cellulose triacotate carrier ^ and dried, whereby test samples were obtained «

For comparison, a control sample was prepared in the same manner as described above, except that the compound mentioned below was used, which has a similar structure to the compounds shown in Table 2, but does not contain any electron-withdrawing substituents.

Control connection:

The individual samples were then developed without exposure for 50 seconds at 34 ^° C. in an automatic developing machine using the developer of the following composition I;

- 11 -

209851/1019

Developer I:

Sodium sulfite 70 g

Hydroquinone 10 g "

Boric Anhydride - "1g

Sodium carbonate (ionohydrate) · '. "' 20 g

1-phenyl-3-pyrazolidone 0.35 g

Sodium hydroxide 5 g

5-methylbenzotriazole 0.05 g

Potassium bromide 5g.

Glutaraldehyde bisulfite. 15 g

Acetic acid '"- ~ 8 g

V / water except for - 1 liter - The samples treated in this way were each uit nitric acid

treated, and the dissolved therein per 100 cm of each sample

Amounts of reduced silver were measured using a Perkin-Elmer atomic absorptiometric apparatus, Model 303 » determined to reduce fogging in the individual samples to compare.

In addition, the individual samples were made according to the method JIS-K-7604 sensitometrically examined their sensitivity to compare.

The results obtained are summarized in Table 2. The sensitivity is given as a relative value, the sensitivity of sample no. 1 also being used. ^#

-12 -

209851/1019

- 12 - link lot
(per Ag X
1 mole) must be used to , if that 2221111 Has recording material the said one considerably TABLE 2 No _ that occurs worse sensitivity photographic . On the other hand, in the samples according to Sample no. Control ver
binding 200 mg Veil (crowd
Silver prop
100 cm of the
Probability the invention Effectively prevents fogging, (D Il 1,500 mg 14.8 mg 100 without the Properties adversely (2) link
Number 1) 100 mg 13.7 mg 97 be flowing. (3) It 150 mg 5.1 mg 32 ' (4) link
No. 2) 150 mg 3.3 mg 98 • (5) link
No. (5) 15 mg 2.0 mg 91 . - 13 - (6) link
No. (8) 250 mg 2.9 mg 94 (7) link
No. (12) 150 mg 1.8 mg 88 (8th) link
No. (13) 150 mg 3.9 mg 96 (9) link
No. (14) 200 mg 3.2 mg 95 (10) link
No. (15) 250 mg 3.0 mg 93 (11) it can be seen that the 3.4 mg 97. (12) dung with no electron-attracting 3.7 mg 96 From table 2 large amount conventional connec- to prevent Gruppo in IlolekUl in the haze formation preserved photographic Recording material in an automatic development machine is developed, and that containing this compound photographic

209151/1019

Example 2

A silver iodobromide emulsion containing 3 % silver iodide; was subjected to the usual second ripening process and then " ^{.. · sensitized by adding 3» 3 f} , eT-riethylthiacarbocyaninbroinid color-s'. An aqueous 1,2-benzo-5-methyl-7-hydroxy was added to the emulsion treated in this way -3,4,7a-triazaindene solution, formalin, and saponin were added, and then the emulsion was coated on a cellulose triacetate support and a polyester support, respectively, from samples No. (13) and No. (.14), respectively -

In addition, the emulsion described above was before the Compound No. (3) was applied to the support in an amount of 150 mg per mol of silver halide. Afterward this emulsion was coated on a polyester support and then dried to obtain Sample No. (15) «

These samples were developed with the above-mentioned ENTV / iekler I 30 seconds at 40 ⁰ C. In addition, the samples were each stored for 5 days in an atmosphere with a temperature of 55 ^° C. and a relative humidity of 5 % and then developed for 4 minutes and 30 seconds with a developer of the following composition at 20 ^° C.

Developer II:

Monomethyl p-aminophenol sulfate 3.5 g

Sodium sulfite (anhydrous), 6Og ⁷

Hydroquinone 9g

Sodium carbonate (monohydrate) '53 g

Potassium bromide 4 g

Water up to 1 liter

The development was carried out without using an automatic development s machine carried out.

- 14 -

Subsequently, the haze and the sensitivity of the samples enjoyed. The results obtained are summarized in Table 3. Therein is the sensitivity as relative value given, the sensitivity of sample no. (13) being 100 as a basis.

TABLE 3

Fresh sample developed After 5 days of storage with developer I 30sek. developed with development 40 ° C ler II 4 min. And 30 sec.

veil Sensitive
speed at 2O ⁰ C Sensitive-
speed sample
No. 0.11 100 veil 100 (13) 0.42 107 0.23 97 (14) 0.12 102 0.42 101 (15) 0.23

It can be seen from Table 3 that the compound used in the present invention has an excellent effect in terms of showing haze originating from the polyester backing and furthermore without deterioration in photographic properties of the recording material prevents fogging when the recording material undergoes high-temperature high-speed development exposed and stored at high temperature.

Example 3 '

A silver iodobromide emulsion containing 1.5% Si, lber iodide was subjected to the usual second ripening process and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added. In addition, formalin, saponin, etc. were added to the emulsion and then divided into two equal portions. One sample was left unchanged. Compound No. (7) was added to the other emulsion in an amount of 140 mg per mol of silver halide. These emulsions were respectively

- ■ 15 -

209851/1019

applied to cellulose triacetate carrier and dried, samples No. (16) and Mr. (17) were obtained. The so The samples produced were developed with the developer I mentioned above. Then haze and sensitivity were meiBe. The results obtained are shown in Table 4 compiled, in which the sensitivity is given as a relative value, with the sensitivity of the control sample No. (16) is set at 100.

TABLE 4

Immediately developed with developer I.

After 6 months of -La- .. ____ _<ge tion with decision _':

45 sec. At 36 ° C 90 _n SeJc. at '^ T ^ LS ⁰ ^ 5 ^un "developed 36 ^G C ^{ent- üen Dei} ^ ^{ü enx} "

wraps

wraps

Schle- sensation- Schle- Em- Veil

Reliability of the p2Lnd sample bin-

No. dung ^ «» _ «_ keit ^ ___ _____

(16) None

(17) Connect
manure
No. (7)

0.18
0.12

100
100

0.35 0.22

0.26 0.20

sensitivity

100 100

From Table 4 it can be seen that In the sample according to Invention, the fogging could be successfully prevented and even then the sensitivity "does not deteriorate." if developed at high temperature or developed after long storage at high temperature,

Example 4 '.......

A silver iodide bromide emulsion containing 3 mol % silver iodide was subjected to the usual second ripening process and then 1 ^ -Benzo-S-methyl ^ -hydroxy-JjA ^ a-triazaindene and 1-phenyl-5-mercaptotetrazole were added. In addition, the emulsion was made with formalin, saponin and the like. moved and on «intn

f6

2OSISWIOIt

Cellulose triacetate carrier applied and dried, doing an emulsion layer on the carrier.

In addition, a 5% gelatin solution was prepared as a protective layer-forming solution and divided into several equal parts. The compounds listed in Table 5 were added to each of these solutions, applied to the emulsion layer described above and then dried, whereby test samples were obtained. The samples thus prepared were developed in an automatic developing machine as described in Example 1, and fog and sensitivity were measured. The results obtained are summarized in Table 5.

link TABLE 5 veil
(Lot
Silver prop
100 cm the
Sample) Sensation
lich
speed sample
No. No Quantity (per
Liter of
Protective layer
Solution) 14.0 100 (18) link
No. (3) - 1.8 96 (19) link
No. (4) 200 mg 2.0 97 (20) link
No. (6) 200 mg 2.4 104 (21) link
No. (9) 200 mg 2.7 101 (22) 200 mg

It can be seen from Table 5 that the compounds according to the invention also have an excellent anti-fogging effect then show when they are incorporated into protective layers.

Patent claims:

209851/1019

Claims (2)

454 Applicant: Konishiroku Photo Industry Co., Ltd. 1-10, 3-iChome, Nihonbashi-Muro-machi, Chuo-ku, Tokyo, Japan Sankyo Company Limited, 1-6, 3-Chome, NihonbasM-Hön-cho, Chuo-ku, Tokyo / Japan. Light sensitive photographic recording material Claims Light-sensitive photographic recording material with at least one silver halide emulsion layer, characterized in that it is in at least one layer a compound of the general formula X " V ^R 4 J wherein X stands for P or N, R _-1 , R ₀ , R-, and R _A each mean an alkyl, aryl or aralkyl group, where at least one of the radicals R ^> Rp »R, and R ^ a Represents aryl or aralkyl group with an electron-withdrawing substituent, and X ~~ represents an acid anion,
contains. 2. Recording material according to claim 1, characterized in that that as a compound of the formula I there is a compound of the formula - 2 - 209851/1019 JPi wherein R _{R is} an alkyl or phenyl group, R _r is NO ₂ , CN or Cl, and η is Ir 1 or 2, contains. Recording material according to one of Claims 1 or 2, characterized in that as a compound of the formula I one of the compounds Ur mentioned by way of example. to No. 15 contains. Recording material according to one of Claims 1 to 3, characterized in that it contains a polyester film carrier as the carrier. Recording material according to one of Claims 1 to 4, characterized in that it is the compound of the formula _2 I. in an emulsion layer in an amount of 10 to -5
10 moles per mole of the silver halide contained in the emulsion layer. Recording material according to one of Claims 1 to 5, characterized in that it contains the compound of the formula in a non-emulsion layer in an amount of 10 to 10 mol per square meter of the non-emulsion layer. Dr.T / hu 209851/1019