DE2033815A1 - Photosensitive silver halide photographic material - Google Patents

Description

Applicant Konishiroku Photo Industry Go., Ltd.

Iiiclite-sensitive, photographic, silver-balogenide-containing material

The present invention relates to a photosensitive photo graphic material containing silver halide, which is also a compound of one of the general formulas given below as Antifoggant in combination with 4-Hydrocyc-6-methyl-1., 3 » Contains 3 <tf »7-tetrazainds. The present invention lies the task is based on a light-sensitive, silver halide-containing to produce photographic material having excellent prevention properties Shows fogging, especially when it is subjected to a so-called rapid development treatment, and that is a reduced change in photographic Shows properties in comparison with a usual developing treatment.

In recent times there is a great need for light-sensitive, photographic recording materials which are to be developed quickly in a short time by treatment at high temperature. The photographic recording light-sensitive materials tend to be processed at high temperatures however, to show increased fogging, and the photographic properties are generally

.-, - ■■ -2-

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worsened.

Light-sensitive, photographic imprinting material is sensitized in a known manner according to various sensitization methods such as sulfur sensitization - the editorial sensitization of the edeliaetaLlsenslfellisleruiig aafi the sensitization using τοπ. Polyalfeylenglycolen · Because these methods generally follow ser have _for the properties of the photographic emulsions ttnsJdhtllch 'the Sehleierbildung deteriorate, many types of anti simä ^ veil agents have been used. " typical® examples of such antifoggants are 4-Hydrozy-6-methyl-'t. _f 3i3aC _> 7r-1; etxazaindex and i-phenyl-EJ-mereaptotetrazole, Die zuerat. The named compound has the effect of a silver halide emulsion that is stored in a silver halide emulsion, which is stored in a way that stabilizes it. The second lined "connection, on the other hand, has a high Aatisc & leiereffekt het photographic emulsions önnttelter mach äerea production" Therefore, these l © iä @ m TertimawBgea are generally used together to achieve an official icing effect. " The anti-fogging effect of 4-hydroxy ~ S - = - nsthyl-1 ₉ 3 3i ^ 97 ~ tetrazaindene is, however, impaired at high temperatures, while 1-phenyl-S-mercaptotetrazole has a somewhat special effect. * A fttografiscne Eaalsion is strongly desensitized and is prsttiscli nalirÄBeli1bar _f if it has been mixed with a sufficient amount, as to avoid the formation of fog during high-temperature development. the change in the photographic properties with high-temperature development is greater than with the usual development treatment.

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In view of this fact, extensive investigations have been carried out with regard to photosensitive silver halide photographic emulsions capable of doing so are successful not only according to the rapid development method, but also with a common development method to be developed. It has now been surprising found that a photosensitive, silver halide-containing photographic emulsion containing at least one of the compounds of the following general formulas (I), (II), (III) and (IV) in combination with 4-hydroxy-6- »ethyl-1,3» 3 «*» 7-tetrazaindene contains, a remarkably lower desensitization than a conventional photographic emulsion shows as well as a high anti-fogging effect not only in a usual development, but also with a high temperature development. In addition, the change in photographic properties is extremely small

The present invention accordingly provides a photosensitive, silver halide-containing photographic material which is characterized in that it contains 4-hydroxy-6 ~ methyl-113 » 3q £> 7-tetrazainds and at least one compound of the following general poreein (I), (II), (III) and (IV)

(I)

- A

(II)

S-A-f X

-4.

BAD ORiOfNAL

009883/162 8

(in)

(IV)

K-

..Λ

where R ₁ and R _{2 are} each alkyl or hydroxyalkyl groups with 1-48 carbon atoms § R _{5 is} an alkyl or hydroxyalkyl group with 1-18 carbon atoms or an aryl or aralkyl group $ X is an anion? Z is a non-metallic group which is required to form the heterocyclic ring together with the I atom j A is an alkyl, alkenyl, alkynyl, aryl or aralkyl group? B - (CHg) _n -, -6H ₂ O (CHg) _n OCH ₂ "- *

CH-, -CH ₂ -O-CH ₂ -, -CH ₂ CH ₂ -S-CH ₂ CH ₂ -, -GHgO.CHg

CH ₂ -S-CH ₂ CH ₂ -OCH ₂ - or -CHgCOCO.CHg-, where η is an integer from 1-10,

contains.

»Substituted or unsubstituted

The compounds of the above general formulas are known as sensitizers, which is disclosed in US Pat. No. 2,288,226, and scarcely show any anti-fogging effect. However, when used in combination with 4 ~ hydroxy-6-methyl-1,3,5 <** 7-tetrazaindene, they exhibit an excellent preventing effect the Schleierb £-making due to an interaction of this compound with what% from the following examples becomes apparent.

The processes for preparing the compounds of the above general formulas have already been described several times in the literature. The process for the synthesis of the compounds of pyridines and alkyl dihalides is described for example in "Journal of the American Chemical Society ^88, J8, 988 and" Annals of Chemistry ", 121 _t 254. The method of synthesizing c_

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of quaternary salts from xylene dihalides is obtained in "Reports", 34, 2089. The method for the synthesis of Compounds of alkylamines or I ^ ridines and alkyl halides is described in "Industrial and Engineering Chemistry", £ 5, 1022, "Chemical and Engineering News" ^ P-, 1282 and "Journal of the American Chemical Society", 68, 753 and 63, H7. The process for the synthesis of the compounds from azoles and alkylene dihalides or alkyl halides is described in U.S. Patents 2,425,774 and 2,694,716.

Typical examples of compounds according to the above general formulas which are effective for the purposes of the present invention are named below: -

009883/162 8

CH,

CH CH,

'^ N - C Br

(2)

Cl

2, II
Cl

^G 12 ^H 25

Br

(6) CH,

Eq

CH

CH

OH

(8) CH,

CH,

CH

CH, I ³ -N- C10 _y

CH ₅

(10)

CH

Cl

(12)

C ₄ H ₉ Br

- CH ₂ O - (CH ₂ ) g _{- OCH 2} > N

ClO, ClO.

009883/1628 "7-

CH

CH ₀ Br

[-M-f \

- N

CH,

Br

GlO

CH,

OH ₂ -

ClO,

OH

HO- CH ₂ -CHH ₂ C HOCH ₂ CH-HpG ^ -N -

HIGH ₂ -CH -Ϊ

OH

S'CH ₀ -CH ₀ -N ² OH

CH ₀ CHCH ₀ OH ^{2 2}

/.CH ₀ CHCH ₀ OH i; ^{2 2}

OH

CH

GH,

f:

H -

I. Br

J «IT

I - ^ LrJtI,

N <T

I ^ CH,

Br. '■ *

ιέ

GH

- (CH ₂ ) ₆ - CH ₂ -

■ ir

0SO ₀ -C> -CH

CH, CF '^

CH

3H

- CH ^ -Ο

Ι
ClO,

CH ₀ - N

² I.

CH

I ClO -8-

00 9883/16 2

(20) C ₈ H ₁₇ C ₈ H ₁₇

CH ,. Γ ¹¹ I i> CH.

^ N _{---- CH 2} ^ COOO-CH ₂ N <_ '

CH, I I CH,

* Br Br ^

- H ₀ C - 0 - (CHjfl - 0 - CH ₀ , 2 Zo ^,

Br "Br

(22) CH CH

CH I ³ I J.CH

Br Br

23 CH

CH1

^ N - CH ₉ OCH ₀ CH ₀ - S - CH ₀ CH ₀ OCH ₅ - N

/ -, 2 2 2 2 2 2 y oh

3 Br Br ^

-The train · the above-mentioned compounds and the 4-hydroxy ~ 6-methyl-1 _t 3 '5 * e7-tetrazaindene to the FOTOGRAFIS & en silver halide emulsion may ^ examples, in the form of aqueous solutions ₉ alkali solutions or alkoholieeaen solutions take place, wherein the compounds are either each alone or in combination with one another are added to the emulsion. The added amounts of 4-hydroxy-6-ethyl-1,3t3oC »7-tetrazaindene and the compounds of the above general formulas can be 0.05 to 6.0 g or less than 1 g per 100 g, based on the silver halide. These compounds can also be incorporated into any layer that makes up the light-sensitive, photographic recording material, such as the protective

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layer ^ an intermediate layer! a filter layer or any Layer containing gelatin. Also in these cases the amounts of the compounds to be added are preferably in the abovementioned ranges · in each of the abovementioned ranges 3? ÄlIe can connect the connections in any arbitrary Step is added during each step of the preparation of the photographic light-sensitive materials will.

Photosensitive! photographic materials containing silver halide are very stable even when subjected to development processing are exposed to high temperatures for a long period of time. They are ideally suited for rapid development. aside from that the photographic recording materials have excellent photography properties even when under normal Development conditions have been dealt with. you will be also less adversely affected by the developing conditions and have the property of always being stable photographic Properties can be achieved.

The invention is further illustrated by the following examples.

example 1

A photographic selatine silver halide emulsion containing 60 g of silver iodobromide in which the amount of silver iodide is 1.5 mol # was subjected to gold sensitization in the second ripening process. When the ripening was complete, the emulsion was divided into five equal portions. One serving was used as a control sample. The four other portions were each mixed with the compounds indicated in Table 1. The emulsions were each coated on a polyester film support and dried to prepare samples. The samples thus prepared were treated according to the sensitometric method regulated in JIS-K-7604. The veil and the relative sensation became _i ₀ - _. 009883/162 8 ~

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- to - sasamiöenge- aimi in Ta- measured * The in S & belle 1 obtained results The compositions of the developers that are used are hereinafter referred to as »The Entloklungsbedliiguiigeii ■ 70 g Belle 1 specified. 10 g Developer (I); Ig. Sodium sulphite 10 g Hydroquinone 0.35 g Boric anhydride 5 g Sodium carbonate (monohydrate) 0.05 g 1-phenyl-1,3-pyrazolidone 5 g Sodium hydroxide 15 g 5-methylbenzotriazole S g Potassium bromide 1 ZdLter Glutaraldehyde bisulphite acetic acid 3.5 g Water except for 60 g Developer (II) ·. 9.0 g Hetol 53 ε anhydrous sodium sulphite ■ 4.0 g Hydroquinone - 1 mter Sodium carbonate (monohydrate) -11- Potassium bromide Water except for

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O CO OO

Added «
lot
(ng) - 11 -
Table 1 rtl. Sensitive
speed After development with.
Developer II at 20 ^° C
while from min. rel. Sensitive
speed • - 100 veil 82 750 After development with
Developer I at 40 ^° C
for 30 seconds 97 0.08 80 50 Sole eggs 70 0.07 83 Controls 750
50 0.31 72 0.09 75 Connection (A) 750
30th 0.25 48 0.07 41
-12- Connection (21) 0.21 0.05 Connection (A)
Connection (21) 0.08 Connection (A)
Connection (B) 0.06

O CO OO CDO

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

It can be seen from the table that when the compound (21) is used alone, it has little anti-squint effect however, it shows a very remarkable effect when it is high-temperature developing treatment ._n Combination with the compound (A) is used, and there is no decrease in sensitivity even with a normal development treatment, so that the photographic light-sensitive material according to the invention is excellent possesses photographic properties.

Example 2

The same emulsion as used in Example 1 was divided into nine equal portions. A portion was used as a control sample. The remaining eight servings were each given the antifoggants listed in Table 2 offset. These emulsions were each coated on a polyester film support and then dried, whereby samples were obtained. The samples treated in this way were treated in the same way as described in Example 1, the results compiled in Table 2 were obtained.

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-13-

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control Added
lot
(mg) - 13 -
Table 2 relative sens
opportunity veil relative sens
opportunity Connection (A) - 100 0.08 81 Connection (A)
(B) 750 91 0.06 80 Connection (1) 750
20th 51 0.06 4b O
CD Connection (A)
(D 55 90 0.09 83 9883/1 Connection (6) 750
35 After development with awake development with
Developer (I) at 40 ^° C. Developer (II.) At 20 "θ
for 30 seconds for 4.5 min. 87 0.06 80 CD
CD Connection (A)
/. (6) 40 veil 82 0.09 83 Connection (17) 750
40 0.28 85 0.07 81 Connection (A)
(1.7) 75 0.20 85 0.07 81 750
75 0.09 81 0.06 79 0.25 • 0.09 0.20 0.09 0.23 0.06

-H-

The developers (I) and (II) mentioned in the table and the Compounds (A) and (B) are the same as in Example

Aub the table iat it can be seen that di @ samples according to the present Invention have excellent photographic properties and that they can be used both in rapid evaporation treatment and are free from a reduction in sensitivity even with normal development treatment, they have beneficial anti-fogging effects show and the photographic properties are less changed.

Sponsor claims

009883/1628

Claims (2)

2 each denote alkyl or hydroxyalkyl groups with 1-1 θ carbon atoms; R is an alkyl or hydroxyalkyl group of 1-18 carbon atoms, or an aryl or aralkyl group; X is an anion; Z is a non-metallic group required to form the heterocyclic ring together with the H atom} A is an alkyl, alkenyl, alkynyl, aryl or aralkyl group; B - (CH ₂ J _n -, -CH ₂ O (CHg) _n OCH ₂ -, -CH ₂ -Z ^ U-CH-, -CH ₂ -O-CH ₂ -, -CH ₂ CH ₂ -S-CH ₂ CH ₂ -, -CH ₂ CCH ₂ CH ₂ -S-CH ₂ CH ₂ -OCH ₂ - or -CHgCOCO.CHg-, where η is an integer from 1-10,
contains. * substitute arte or unsubstituted -16- 009883 / T6 2 8 Toooo 2. Photographic material according to claim 1, characterized in that that the compounds in at least one of the layers: emulsion layer, intermediate layer, protective layer and / or filter layer are present. 009883/1628