DE2040876A1 - Light-sensitive photographic recording material containing silver halide - Google Patents

Description

Applicant: Konishiroku Photo Industry Co., Ltd., Tokyo

Light sensitive photographic recording material containing silver halide

The present invention relates to a photosensitive photographic recording material containing silver halide, the compounds of the general formulas (I), (II), (III) and (IV) given below as antifoggants in combination with 4-Hydroxy.-6-methyl-1,5 »3a, 7-tetrazaindene contains. Also concerns the present invention the use of a benzotriazole derivative of the general formula (V) as an additional Component.

It is an object of the present invention to use light-sensitive, silver halide-containing photographic recording materials produce the excellent properties with regard to the prevention of fogging have, especially if they are subjected to a so-called rapid development treatment, and which has a smaller change in photographic properties in comparison with a conventional development treatment.

In recent times there is a great need for light-sensitive, photographic recording materials obtained by treatment Developed rapidly in a short time at high temperature should be. The photographic recording light-sensitive materials tend to be processed at high temperatures

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however, it tends to show increased fogging, and photographic properties are generally deteriorated.

Photosensitive, photographic recording materials are in known to be sensitized by various sensitization methods like sulfur sensitization, reductive sensitization, noble metal sensitization and sensitization using polyalkylene glycols, etc. In general, however, the aforementioned sensitization methods work that there is a tendency for the properties of the photographic recording materials to deteriorate there is increased fogging. Therefore, antifoggants have typically been used. As an anti-fogging agent a large number of compounds are known. Particularly typical) Examples of such compounds are 4-hydroxy-6-methyl-1,3,3a 7-tetrazaindene and i-phenyl-5-mereaptotetrazole. The former Compound acts to stabilize the fog of silver halide photographic emulsion that is in storage. It has a relatively low anti-fogging effect in photographic emulsions which processed immediately after their manufacture. On the other hand, the second compound mentioned has a high anti-fogging effect in the case of photographic emulsions, immediately after their manufacture. Therefore, in general, these two compounds are used together to achieve an anti-fogging effect. The anti-fogging effect of 4-hydroxy-6-methy1-1,3,3a, 7-tetrazaindene however, is affected by high temperature development, while the 1-phenyl-5-mercaptotetrazole has a strong desensitizing effect. Therefore it becomes a photosensitive On drawing material that this connection in a sufficient Contains amount to prevent haze at high temperature Avoid development is largely desensitized and useless for practical purposes. Accordingly is for conventional, light-sensitive photographic recording materials, which contain these fogging agents, the change in photographic properties great, ao that ea

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it is difficult to foresee a sufficient anti-fogging effect ^

In view of this matter, extensive studies have been made on photosensitive silver halide photographic recording materials capable of being successfully developed not only by the tendon developing method but also by a common developing method. It has now surprisingly been found that a light-sensitive, silver halide-containing photographic recording material which contains at least one of the compounds of the following general formulas (I), (H) ₉ (III) and (IV), which are mentioned below, in combination with 4-hydroxy -6-methyl-1,3 »3a, 7-tetrazaindene and in some cases with a compound of the general formula (V), shows a noticeably lower desensitization than a conventional photographic recording material and a high fogging effect both in high-temperature development and in a common development.

The present invention accordingly provides a photosensitive, photographic recording material containing silver halide, which is characterized in that it contains at least one of the compounds of the following general formulas (I), (II), (III) and (IV)

R ₂ J ¹

\ / f ^{A (II)}

109810/1578.

R.

R.

R-

-B -

(in)

N-

• Β

(IV)

wherein R ₁ and Rp each represent alkyl or hydroxyalkyl groups having 1 to 18 carbon atoms; R., is an alkyl or hydroxyalkyl group of 1 to 18 carbon atoms or an aryl or aralkyl group; Z is a non-metallic group capable of forming a hetero ring together with the adjacent nitrogen atom; A represents an alkyl-alkenyl, aryl or aralkyl group; B for

^ .— ptj c \ ( pti "\ ηπτί pit // X ptj pu λ put

ρ / γ * '~ ^ HO \ 2' η 2 ~ "'~ ^ -" p— \ / ~~ ^ iIp "> —Oxlp — U — Uilp—,

.CH ₂ -S-CH ₂ .CH ₂ -, -CH ₂ .0.CH ₂ .CH ₂ -S-CH ₂ .CH ₂ .0.CH ₂ - or .CO.CO.CHg-, where η represents an integer from 1 to 10; and X is an anion,

together with 4-hydroxy-6-methyl-1,3 _f 3a, 7-tetrazaindene in at least one of the layers forming the photographic recording material.

The recording material according to the invention preferably additionally contains as a third component in one of its layers a compound of the general formula

(V)

wherein Y represents a hydrogen atom, a nitro group Halogen atom or a methyl group.

The compounds of the above general formulas (I) to (IV) _r

109810/1578

are known as sensitizers, which is written in the USA patent 2,288,226 and other references, and they hardly show any anti-fogging effect. the Compounds of the above general formula (V) are known as antifoggants, but they have a strong desensitizing agent Effects like i-phenyl-5-mercaptotetrazole. If you used in an amount sufficient to produce a sufficient To bring about anti-fogging effect in high temperature development, the desensitizing effect is too strong to still to enable a practical application.

However, if at least one of the compounds of the general formulas (I) and (IV) in combination with 4-hydroxy-6-methyl-1,5, 3a, 7-tetrazindene and further, if desired, with a compound of the general formula (V) can be used excellent anti-fogging effect through effective interaction of these two or three components can be achieved ^ this will be further explained with the aid of the following examples.

Processes for the preparation of the compounds of the above general formulas (I) to (IV) have already been described in many parts of the literature. For example, the process for the synthesis of these compounds from pyridines and alkyl dihalides is described in Journal of the American Chemical Society, 18, 988 and Annalen der Chemie, 121 _t 254. Bin process for the production of quaternary salts from Xyloldihalogeniden described in reports 21t 2089 · Measures for the synthesis of the compounds from alkylamines or pyridines and alkyl halides are described in Industrial and Engineering Chemistry, 4,5, 1022, Chemical and Engineering News, 22 »1282 and Journal of the American Chemical Society, 68, 753 and 6 £, 147 · Process for the preparation of the compounds from azoles and alkylene dihalides or alkylene halides are described in US Patents 2,425,774 and 2,694,716.

Preparation of the compounds of the general formula (T)

100810/157 «

- D -

is described in Reports, _9, 219 and % ^ _t 4028; Annals of Chemistry, 249, 361 and 211, ²⁹ ° " ^and Journal of the American

Chemical Society, 79, 4395 (1957).

Typical examples of compounds of the general formulas (I) Ma (IV) are:

C _{1 o} Hnr

■ j πυ 112 25

CH- I ⁰ ^ I

CH ^^ I ^{1Ö il CH} 3 I.

-7-

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C ₂ H ₅

: N CH ₀ -O = CH ₀

ι - 2 j 2

¹ CH,

ei y

204087ε

C ₂ H ₅

Cl

° 12 ^H 25

Br

(6)

CH.

ci

CH,

CH

CH ₀ -CHCH ₀ OH 2, 2

OH

CH,

CH.

SO ₄ CH ₃

-8th-

CH ₃

CH ₀ -N- ClO. 2 / \ 4

CH ₅ CH ₅

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(10)

(H)

CH ₂ CH ₂ Br

"N

Cl

(12)

C-CH

C ₄ H ₉ Br

(13)

- (CH

ClO,

ClO

(H)

CH.

CH

CH,

N - CH,

Br

CH.

- ν:

Br

-CH

-CH.

(15)

CH. CH,

• Ν

ClO,

OH

(16)

OH

HIGH ₂ CH-H ₂ C

CH ₂ -CH-CH ₂ -OH OH

HIGH ₅ Ch-H ₉ CN-CH ₀ -CH ₀ -S-CH ₀ -CH ₀ -N - CH ₀ -CH-CH ₀ OH

OH /

HIGH ₀ -CH-H ₀ C 2!

OH

ClO CH ₂ -CH-CH ₂ OH

ClO,

OH

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CH.

CIL

-CH,

CH.

(CH ₀ J _1n - N.

'2 ⁷ IO

CH,

Br

Br

OH, -

0'S0 _o -f V-CH.

GH, -

(.19).

- CH ₂ -

CH;

0 - CH ₂ - N _v

ClO.

ClO

CH,

CH,

° 8 ^H 17

N - CH ₂ COCOCH ₂ - N

, CH ₃ ■

CH

Br

Br

^ CH ₂ -O- (CH ₂ ) ₅ -0-0Η ^ Br Br

CH,

CH,

CH,

CH

N - CH ₂ -CH ₂ - Ν!

Br

Br

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- ίο -

(23)

CH

CH

CH,

-N -

Br

CH,

- N

Br

typical examples of compounds of the general formula V:

(24)

CH,

(25)

¹ N '

i
H

N Il N

(26)

Cl

N I!

■ (27)

(28)

(29)

O ₂ N

T09810 / 1S78

To make the above compounds photosensitive photographic emulsions in combination with 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene to give these compounds individually or mixed with each other in aqueous solutions, alkali solutions or alcohol solutions and then added to the emulsions. The amounts of compounds to be added are preferably such that per 100 g of silver halide the amount of 4-hydroxy-6-methy1-1,3,3a, 7-tetrazaindene 0.05 to 6.0 g, the amount of compounds of general formula (I) to (IV) less than 1 g, and the amount of compounds of general formula (V), if used, will be less than 0.3 g. The links can be to any of the layers making up the light-sensitive photographic recording material. Examples of such Layers are protective layers, intermediate layers, filters * - layers, etc. In these cases, too, the quantities to be added lie Connections within the above limits. The compounds can also be used in combination with dyes. Sensitizers, hardeners and similar known photographic additives can be used.

The invention is further illustrated by the following examples.

example 1

A gelatin emulsion with 60 g of silver iodobromide containing 1.5 mol of silver iodide was subjected to gold sensitization in the second ripening process. After the ripening was complete, the emulsion was divided into several equal portions. One serving was used as a control sample. The compounds listed in Table 1 were added to each of the other portions. Then, these emulsions were each coated on polyester film supports and then dried to obtain film samples. These samples were sensitometrically treated according to the method described in JIS-K-7604. The photographic properties of the treated samples were -12-

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- 12 2040876 where developers of the fol- 70 g -13- measured, with those in the table 1 results became: 10 g were holding. The development was under the conditions shown in Table 1 1 g mentioned conditions carried out, 20 g lowing compositions used 0.35 g Developer (I); 5 g Sodium sulfite 0.05 g Hydroquinone 5 g Boric anhydride 15 g Sodium carbonate (monohydrate) 8 g 1-phenyl-1,3-pyrazolidone 1 liter Sodium hydroxide 5-methylbenzotriazole 2.5 g Potassium bromide 60 g Glutaraldehyde bisulfite 9.0 g acetic acid 53 g Water except for 4.0 g Developer (II): 1 liter Metol anhydrous sodium sulfite Hydroquinone Sodium carbonate (monohydrate) Potassium bromide Water except for

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TABLE 1

added
lot
.Ue). 40 ⁰ C icier ti;
30 sec. Development
20 ⁰ C. £ ler (II)
45 min. Control
Connection (A) .750 veil relative em
Ofindliohkent veil relative em
sensitivity Connection (A)
Connection (B) 750
30th • 0.54
• 0.29 100 "
96 0.08 ^;
0.07 85
82 Compound No. ( 21)
Compound No. (26) 50
30th 0.07 48 0.05 45 : Connection no. ' (21)
Connection (A) 50
750 0.22
0.06 ' - 72
55 0.08,
0.04 86
50 Connection no. "(21)
___. Compound No. (26)
Connection (A) 50
30th
750 0.07 75 0.06 75 Compound No. (26)
Connection (A) 50
750 0.04 70 0.04 71 0.05 54 0.04 50 ·

- ■ Η

In the table, the compound (A) is 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, and the compound (B) is 1-phenyl-5-mereaptotetrazole.

From Table 1 it can be seen that when the compounds Nos. (21) and (26) are used alone, less anti-fogging effect or greater desensitizing effect is achieved. However, when the above three compounds are used in combination, excellent ones can be obtained photographic properties can be obtained.

Example 2

An emulsion was prepared in the same way as described in Example 1 and divided into several equal portions. One serving was used as a control sample. the The compounds listed in Table 2 were added to each of the other portions. Then, these emulsions were each coated on a cellulose triacetate film support and dried to obtain film samples. the Samples were treated in the same manner as in Example 1, the results shown in Table 2 being obtained.

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TABEL

(6) added 4O ⁵ Wxeider (l)
G. 30 see. 20 ° ct ° »Τ * 'Γ Γ )
X ^ XJ. J
'4 φ5 min " it; lot
(mgj veil veil relative em
Of indlic hjr ^ fc. control
Connection (A) (6)
(27) 750 O.29
0.22 0.08
0.07 82
80 Connection (A)
Connection (B) (27) 750
• 20th 0.08 0.06 47 Connection no.
Connection no. 40
20th 0.18
0.08 0.08
0.06 81
50 ~ "Connection NrV
Connection (A) 40
750 0.10 0.07 81 Connection no.
Connection no.
Connection (A) 40 '
20th
'750 0.05 0.05 '· I
75 Connection no.
Connection (A) 20th
750 0.07 0.06 49 relative em
pfind 1 i r.bVrats 100
91 49 82
53 85 71 51

»1 G-

In the table are developers (I) and (II) and the compounds (A) and (B) the same as in Example 1.

It can be seen from Table 2 that Compound Nos. (6) and (27) when used in combination with Compound (A) will give a remarkable anti-fogging effect and a lower desensitizing effect, so that excellent photographic properties can be achieved.

Example 3

An emulsion was prepared as described in Example 1 and divided into several equal portions. A portion was used as a control sample. The other portions were each mixed with the compounds listed in Table 3. Then these emulsions were each made on cellulose triacetate film support applied and dried to obtain samples. These samples were made in the same way as Treated described in Example 1. The results compiled in Table 3 were obtained.

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1 0981 0/1578

ΪΑΒΕΕΕΕ 3

- added
lot
(mg) 40 ⁰ C. 5lcler (I)
30 sec. Jiäitwici
..20 ⁰ C. : ier (Ti;
4.5 min. control
Bond (A) 750 veil relative em
Sensitivity Veil relative em
pfindlicbkeifc Connection (A)
Connection (B) 750
30th 0.30
0.26 100
93 0.08
O.OS 82
80 Connection no. (17)
_ Connection ITr. (29) 750 0.06 46 0.05 42 i compound no. (17)
Connection (■ *.) 75
15th 0.23
0.07 85
56 0.07
0.06 80
50 Connection no. (17)
Compound no .. (29)
Text filling (A) 75
15th
750 0.07 81 0.06 79 Connection no. (29)
Connection (A) 15th
750 0.03 76 0.Q3 73 0.06 52 0.05 48

-18-

20A0876 '

In Table 3 are the developers (I) and (II) and the compounds (A) and (B) the same as in Example 1.

It can be seen from Table 3 that Compounds No. (17) and No. (29), when used alone, have one have little fogging effect or a great desensitizing effect. The anti-fogging effect will be greater when they can be used in combination with the compound (A). However, when the compound No. (29) is combined with the compounds No. (17) and (A) is used, not only the anti-fogging effect is increased but also the desensitizing effect is further reduced, thereby enabling excellent photographic properties to obtain.

Example 4

Containing a gelatin emulsion of 60 g of silver iodobromide 5.3 mol # silver iodide was subjected to gold sensitization at the time of the second ripening process. After completion After ripening, the emulsion was divided into several equal portions. One serving was used as a control sample. The other portions were each mixed with the compounds mentioned in the table. Subsequently, these were Emulsions applied to cellulose tetrlacetate film support and then dried to make samples. These samples were treated in the same way as described in Example 1, the results shown in Table 4 were obtained.

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TABEL

(JD CO

added
lot
(mg; Dev
40 ⁰ C. animal (I)
30 Sflfi,, Develop
20 ⁰ C. ler (11)
4.5 a. control
Connection (A) 750 veil relative em
sensitivity veil relative eq
sensitivity Connection (A)
Connection (B) 750
20th 0.33
0.29 100
94 0.08
0.07 84
81 Connection no. (1)
Connection ITr. (25) 35
30th 0 * .08 62 0.06 60 ι Connection no. (1)
Connection (A) 35
750 0.25
0.07 90
60 0.08
0.06 83
58 . Connection no. (1)
ί Compound no. (25)
Connection (A) 35
30th
750 0.09 87 0.07 81 . " Compound No. (25)
Connection (A) 30th
750 0.04 80 0.04 78 0.06 57 0.06 55

-20-

20A0876

In Table 4 are the developers (I) and (II) and the compounds (A) and (B) the same as in Example 1.

From Table 4 it can be seen that the compounds No. (1) and No. (25) and the compound (A), when used alone, have a small antifogging effect or a large one Have desensitizing effects. However, when these three compounds are used in combination, a remarkable one shows up Anti-fogging effect that makes it possible to obtain better photographic properties than in the case in which any two of these three compounds can be used in combination.

Claims ι

1 098 10/1578

Claims (2)

Claims wherein R ₁ and Rg each represent * alkyl or hydroxyalkyl groups having 1 to 18 carbon atoms; R. is an alkyl or hydroxyalkyl group with 1 to 18 carbon atoms or an aryl or aralkyl group? Z is a non-metallic group which commands the formation of a hetero ring old from the neighboring Stiokioff atom A is an alkyl, alkenyl, aryl or aralkyl ftnipye means S for - (CH ₂ ) j, -OH ₂ O (OH ₂ ) _& ΟΟΗ ₂ -, .0.0H ₂ -I-OI ₂ Wi m «im · »Der -OHj.CO.00.OH ₂ - eteht, S« kX res 1 Ue 10 means » mA I 101110/1671 BATH ORIGINAL is an anion together with 4-hydroxy-6-methyl-1,3 _f 3a, 7-tetrazaindene in at least one of the layers forming the photographic recording material. 2. Recording material according to claim 1, characterized in that that there is also a compound of the general formula as a third component in one of the layers (V) where Y stands for »in hydrogen atom, a nitro group, a halogen atom or a methyl group contains TOfllD / 1171