DE1800987A1 - Photographic processing for silver halide photographic photosensitive elements - Google Patents

Description

FATIHfANWXlTI DIPL.INO.w.niimann 1 §00987 DR. M. KOHLIR DIFt-ING. C. OERNHARDT MONCHlN HAMIUIO

55547 «moo MONCHiN October 15, 1968

TIHOIAMMI, KAIPATINT NUtIIAUMITIASIEIt

W. 15 9IV68

Fuji Shashin Movie Kabushiii Kaisha Kanagawa (Japan)

Photographic processing for halogen fiber photographic light-sensitive elements

The invention generally relates to a photographic one Treatment for silver halide photographic photosensitive elements and in particular to a process for Reduction of the formation of fog that occurs when hardening halogen silver emulsion layers.

When photographic photosensitive films, photographic copy papers or photographic photosensitive plates are treated with silver halides after exposure,

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they are generally common prior to developing one Subjected to hardening treatment.

The purpose of the hardening treatment is to prevent mechanical damage to the emulsion layers during processing by increasing the mechanical strength of the emulsion layers of photographic light-sensitive elements; the application of the hardening treatment is particularly effective when the mechanical strength of photographic emulsion layers is originally insufficient. ..photogr aphis before E _m ulsionsschichten during a long period of time to be treated or to be treated in a treatment solution having a high pH or at a high temperature.

The hardening treatment that occurs before the development stage is usually referred to as "pre-hardening", and as the hardening agent for the treatment, an aldehyde used for hardening gelatin is usually used in the photographic emulsion layer by reaction thus capable of, for example, formaldehyde, glyoxal, succinaldehyde, glutaraldehyde or the like.,.

However, although the photographic emulsion layers are effectively hardened for this type of pre-hardening treatment are given these adverse influences to the photographic properties of the photo-

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graphic emulsion layers so wjfcd, for example, the Education.yon development veils increased, the developmental dynasty in reverse development decreased and the coupling behavior changed by couplers in photographic color photosensitive elements.

The object of the invention is therefore to create an improved one Photographic treatment for photographic light-sensitive elements, suitable for treating the emulsion layer said photographic photosensitive elements have sufficient mechanical strength to grant, without the occurrence of the disadvantages described above.

According to the invention there is an improved photographic processing for photographic photosensitive Elements created, being the photographic light-sensitive Elements between a pre-hardening stage and a developer stage treated in an aqueous solution, which is a resore derivative of the general

OH

contains, where Aiind B each is a hydrogen atom, a lower alkyl group, a halogen atom, OR, (where R, represents a lower alkyl group), CORg (where R _{2 represents} a hydroxyl-alkoxyl or NH ₂ group) or SOgR, (where R ^

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represents a hydroxyl, alkoxyl or NHg group),
mean.

Typical examples of resorcinol derivatives of the formula given above are resorcinol, 4-chlororesorcinol, 4,6-dichlororesorcinol, 4-methoxyresorcinol, 4-methylresorcinol and
4-carboxyresorcinol.

The appropriate concentration of the resorcinol derivative depends on the concentration of the aldehyde resulting from the pre-hardening treatment; however, the aldehyde from the pre-hardening treatment can be effectively used at a concentration range of 0> 1 to 100 g / liter of the resorcinol derivative
white away.

■ The aqueous solution for anti-fog treatment can be used in any pH range, but it is particularly effective in the neutral or acidic state. In addition, the resorcinol-containing aqueous
Solution a pH regulator or a buffering agent, e.g. sodium sulfate, borax, acetic acid, sodium acetate, sodium carbonate, sulfuric acid and boric acid, as well as other common ones
Contain antifoggants, e.g. an alkali halide.

The photographic emulsion layer to be processed according to the invention usually contains as a light-sensitive material Halogen silver and as a dispersant for the light

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sensitive material gelatin or a mixture of gelatin and another hydrophilic material of high value Molecular weight. As a support for the photographic emulsion layer For example, a glass plate, a cellulose ester film, a polyester film, or paper can be used.

The method according to the invention is particularly when applied to the treatment of color photographic light-sensitive Inversion elements that are suitably treated at a high pH and for a long period of time and for the treatment of color photographic copier papers, which are preferably treated rapidly at a high temperature be suitable.

When performing the method according to of the invention become photographic photosensitive members after being subjected to a pre-hardening treatment in an aqueous solution containing the above resorcinol derivative, together with others if necessary Additions, contains, treated and then subjected to the usual subsequent treatments in the order in which they are used.

In the method according to the invention, the formation of development fog is less compared to one

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usual photographic treatment, with a decrease does not occur in the development density and the coupling ability of couplers in color photographic photosensitive elements.

The invention is illustrated below by way of examples explained in more detail.

example 1

A sufficiently color sensitized gelatin-iodobromide silver panchromatic emulsion layer deposited on a CellulGEB acetate film was formed using a sensitometer exposed and subjected to the following photographic treatments at 40 ° C.

Treatment . Duration ( seconds)

Pre-hardening 55

Washing 10

Haze Prevention Treatment 45

To wash . 20th

Development 50

Interruption 10

Fixation j50

Washing 90

The compositions of the treatment solutions used in the above treatments are given below:

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VorhardenunKSZusainrnensetzunp: '

Sodium bisulfite

Formalin (37 follow aqueous solution) Borax

Sodium sulfate

Potassium bromide

water

1 g 15 ml 5 g 50 g

2 g

1 liter

Balance on anti-fogging composition;

The resorcinol derivatives listed in the table below were each added to one liter of an aqueous solution containing 5 g of glacial acetic acid and 1 g of sodium acetate.

£ ™ ^{u <} * addition Amount (g) 1 (control) none _ 2 resorcinol VJI j5 resorcinol 10 4 4-chlororesorcinol 5 5 4-Chlorresorein 10 Developers Amount (g) Metol (methylaminophenol) VJi Hydroquinone 2 Sodium sulfite 70 Sodium hydroxide 1 Sodium carbonate t-monohydrate 41 Potassium bromide 2 VJasser rest up 1 liter

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Interrupt solution Rest on 15 ml Glacial acetic acid 1 liter water Fixing solution 150 g sodium thiosulfate Rest on 15 g Sodium sulfite 1 liter water

The photographic properties of the above The test films treated are listed in Table I below.

Table I.

Ver
seek veil
No. 0.36 Relative
"Sensitive
speed Gamma value 1 (con
trolls) 0.27 2.20 0.32 2 0.25 2.30 0.33 3 0.26 2.31 ' 0.33 4th 0.23 2.32 0.35 5 2.32 0.36

In Table I above, the relative sensitivity is represented by the logarithmic reciprocal of the exposure amount corresponding to a density of 0.1 above haze.

From the above results it is clear that by using the anti-fog. treatment according to the invention the formation of development ·

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shiver was effectively prevented and the sensitivity and the gamma value has also been increased.

Further, since the pre-hardening treatment is put to practical use by using the anti-fogging bath can, in order to improve the mechanical strength of the emulsion layers, can use the photosensitive elements treated at a high temperature without occurrence of malfunction.

Example 2

Eire sufficiently color-sensitized panchromatic Gelatirie halogen silver Emulsiorisschiüt, which was formed on a polyester film 'has been exposed by a sensitometer through a silver wedge, and then the following photogi ^ Hischen treatments at 27 ⁰ C with the exception of the drying subject, the latter at 58 ⁰ C was executed.

treatment Duration (seconds) Pre-hardening 60 To wash 30th Haze prevention treatment 60 V / a see 30th First development 210 To wash 30th bleaching 120 To wash 50 Clean 60

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Washing ^ O

Second development 120

Washing 30

Freeze 90

Washing I50

Drying I80

The compositions of the above treatment Treatment baths used are indicated below.

Pre-hardening composition;
Same as in example 1

Anti-fogging composition

The resorcinol derivative shown in Table II below became one liter of an aqueous solution containing of 4 g of sodium acetate, 5 ml of acetic acid and 0.7 g of potassium bromide admitted.

First and second developer

0.8 g / liter of potassium thiocyanate was added to that in Example 1 specified developer added.

Pond solution :

sulfuric acid Rest on 5 ml Potassium dichromate 4th G water 1 liter Re irtaungjs ζ us ammens e t ζ unß Remainder * Sodium sulfite
TI G S '
water liter Fixing solution

same as in example 1

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The results obtained when performing the above Treatments obtained are listed in Table II below.

Table II
Attempt _Zußatz amount _{reverse osmosis} hrdichte

1 (control) none - 1.12

2 4-CHorresorcinol 2 1,4 ^

3 4-chlororesorcinol 5 1.46

4 4-chlororesorcinol 10 1.48

As clear from the above results It can be seen that the reverse density was due to the application of the anti-fogging bath according to the invention and therefore better photographic properties in the photographic films thus treated are obtained in spite of the application of the pre-hardening treatment. Moreover, during the treatment according to the invention mechanically damages the surface of the emulsion layer to a lesser extent and the drying load or performance could be reduced will.

Example 3

A full color photographic multilayer film otempfindllchkeit by application to a cellulose acetate a gelatin Jodbromsilber emulsion with an ^R, a gelatin Jodbromsilber emulsion with a green sensitivity,

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a yellow filter layer containing fine colloidal silver particles with a blue absorption capacity and a gelatin-iodobromide silver emulsion with a blue sensitivity was prepared in the order given, was exposed through a silver step wedge using a sensitometer and then ^{subjected to the following photographic treatments at 24 °} C:

Treatment duration (min.)

Pre-hardening. 1

Washing 1

Anti-fog treatment 1

Washing '1

First development 5

Washing 2

Reverse exposure at 200 CMS (red light) from the

side of the film

Cyan color development 5

Washing 2

Reverse exposure at 200 OMS (blue light) from the

EmulsioH side of the film

Yellow color development 5

Washing 1

Second development 1

Washing 1

Reverse exposure (white light) at 2000 CMS from the opposite sides of the film

Magenta color development 5

Washing 5

Bleach 2

Washing 1

Fix 2

Washing 2

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The treatment solutions used in the above treatments are explained in more detail below.
Precure composition; Same as in example 1

Anti-fogging composition;

The resoncin derivatives given in the table below were a Ljfer an aqueous solution with a Content of 8 g boric acid, 0.2 ml sulfuric acid and 0.8 g Potassium bromide added to form the anti-fog bath.

Trial no. Additional amount (κ)

1 (control) no _ 2 Resorcinol 5 Resorcinol 10 4th 4-chlororesorcinol 5 5 4-chlororesorcinol 10 First and second black and white developers Same as in example 2 Cyan color developer

! {atrium sulfite 5 * 0 g

2-amino-5-diethylaminotoluene sulfate 0.6 g sodium carbonate monohydrate 15.0 g

Potassium bromide 0.5 g

Potassium iodide (0.1 μl aqueous solution) 5 ml

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1,5-dihydroxy-2,6-dibromonaphthalene Sodium hydroxide

water

Rest on

1.2 g 2.0 g 1 liter

Yellow color developer

sodium sulfite 5 , 0 G G Ν, Ν-diethyl-p-phenylenediamine sulfite 2 , 5 G G Potassium bromide 1 , 0 G G Potassium iodide (0.1 sequence aqueous solution)
XjJ ~ -Benzoyl ~ 4- {p-toluenesulfonamido) -
acetanilide 5
1 , 0
, 2 ml
G G Sodium hydroxide 2 , 5 G G Water rest on 1 liter ml Magenta color developer liter Sodium sulfite 5 , 0 2-Amino-5 "diethylaminotoluene hydro-.
chloride 2 , 0 Potassium bromide 0 ,8th l-phenyl-3- (m-nitrobenzoylamino) -
5-pyrazolone χ. _Λ Sodium hydroxide 2, , 0 n-butylamine 5. , 0 Water rest on 1 Bleaching composition

Potassium ferricyanide

Potassium bromide

borax

Boric acid

water

Rest on

100 g 20 g
2.0 g 1.0 g 1st liter

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Fixing together etzunp ;

Sodium thiosulfate rest on 150 g Sodium sulfite 10 g water 1 liter

The results are in Table III below listed.

Table III 2.95 Blue density Attempt no. 3.31 2.90 Reverse density 3.34 3.33 1 (control) Red density green density 3.33 3.40 2 3.05 3.40 3.45 3 >, 39 3.48 4th 3.40 5 3.4 3.44

It is clear from the results of the above table that by applying the anti-fog treatment According to the invention, the coupling density was increased and that no adverse effects on the photographic properties were observed, i.e., there was no contamination and no decrease in sensitivity observed.

Example 4

A commercially available color photographic printing paper was prepared by a Sensitoneter · ^ "> olichtet and subjected to the treatments indicated below at 2O ⁰ C:

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Treatment I.

Color developing washing

Lead fixation washing

Hardening

To wash .

Buffer treatment washing

Stabilization drying (at 58

Duration (min.) 5

8 10

The compositions of the above treatments solutions used are given below:

Color developer

N-ethyl-N-hydroxyethyl-p-phenylene-

diamine sulfate ■ 7.5g

^ hydroxylamine sulfate. OJ g

potassium carbonate 100 g

Potassium bromide 1 g

Sodium sulfite (anhydrous) 4.5 g

Sodium tripolyphosphate 1 g

Water rest to 1 liter

Bleach-fix composition

Iron salt of ethylenediaminetetra-

vinegar mre 5 ° g

Sodium carbonate (anhydrous) 2.5 g

Sodium sulfite (anhydrous) 10 g

^ altrium thiosulphate (anhydrous). 200 g

Water rest to 1 liter

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Curing composition

Tetrasodium salt of ethylenediaminetetraacetic acid 0.5 g

Sodium carbonate ■ 10 g

Sodium sulfate 50 g

Formalin (37 # solution) 50 ml

Sodium bisulfite 4 g

Wasaer rest on 1 liter

Buffer solution

Tartaric acid 10 g

Borax 25 g

Water rest to 1 liter

Stabilization composition;

Brightener (Tinopol) (trademark, manufactured by Geigy AG) 4g

Sodium dihydrogen phosphate 4 g DÜjßtriumhydrogenphosphat 2 g

fetasodium salt of ethylenediaminetetraacetic acid 1 g

Water rest to 1 ^ iter

In practicing Treatment I, good photographic qualities became de ^ hotographic Copy obtained, but this was accompanied by the disadvantage that the copy paper for a long period of time had to be treated as shown above.

In order to shorten the treatment time, the copy paper was therefore treated at 35 ° C. (treatment II), with however in this case a so-called wrinkle grain formation

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the emulsion layer occurred, thereby reducing the technical merit the copy paper has been reduced

There was therefore a hardening treatment before the 3-color development carried out (Treatment III) # Here, instead of the hardening treatment of Treatment I, the copy paper was used for 60 seconds in a hardening bath having the composition given below before color development treated. ·. .

Hardening composition;

Formalin (3% aqueous solution) 20 ml

2,5-dimethoxytetrahydrofuran 4 ml

Sulfuric acid ■ 2 ml

Sodium sulfate '100 g

Potassium bromide 2g

Borax 5g.

Water rest on 1 later

However, when Treatment III was practiced, developmental fog became remarkable to a considerable extent formed although the mechanical strength of the emulsion layer was sufficiently improved, and accordingly was the technical value of the copy paper as practiced in Treatment II.

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Treatment IV of the present invention was therefore carried out using the anti- fog treatment, and according to this method, better photographic properties than treatment I were obtained. Moreover, as shown below, the copying paper could be treated for a short period of time (at a higher temperature) while maintaining sufficient mechanical strength of the photosensitive insulating layer. This treatment was carried out at 38 ⁰ C.

Treatment IV Duration (see.) Hardening 60 To wash 30th Haze prevention treatment 60 To wash 30th Color development 100 To wash 30th Lead fixation 140 To wash 30th buffering 40 To wash 30th stabilization 40 Drying (at 50 ° C)

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The Schleierver u- «tungsbad tea used in this process consisted of an aqueous solution with a content of 10 g / liter of 4-chlororesorcinol and 0.5 g / liter
Potassium bromide. Furthermore, the hardening bath was the same as in treatment III *

The fog densities of the copier papers treated according to Treatments I, II, III and IV are as follows Table IV compiled.

Table IV

treatment Sole protectors jrannouncement Blue density Red density ( 0.08 0.11 I. 0.08 mm II - 0.20 0.45 "III 0.35 ·. 0.09 O ₁ H IV 0.09 1 example

A gel-elatine-halosilver emulsion layer with a red-sensitive layer, which is based on a cellulose acetate film
was exposed through a silver step portion by means of a sensitometer, and the following
subjected to color treatments at 24 ⁰ O:

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Treatment Duration of treatment (sec. )

Pre-hardening 60

Washing 60

Haze Prevention Treatment 60

Washing 60

first development 210

Washing 60

Reverse exposure at 200 OMS under white light

Cyan color development 210

Washing 60

Bleach 60

Washing 60

Freeze 60

Washing 60

The precure bath and anti-fogging bath compositions used above were the same as in Example 1 and the other compositions were the same as in Example 3 The results obtained are listed in Table V below.

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Of? IG. ^! NAL INSPECTED

Table V

Attempt no

additive

Quantity (S)

Reverse density (red density)

1 (control) no -

2 resorcinol 5

3 4-chlororesorcinol 5

4 ^ -, e-dichlororesorcinol 5 3 4-methoxyresorcinol 5 6 4-methylresorcinol 5

0.55 1.01 1.12 1.10 1.05

It is clear from the above results that by using the anti-fog bath according to the invention the coupling density has been increased considerably.

Example 6

Reverse magenta color development was performed as in Example 5 described carried out »The procedure of Example 5 was repeated with the modification that the magenta color developer shown in Example 3 was used in place of the cyan color developer of Example 5 and the anti-fog compositions listed in the table below came into use.

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The anti-fog bath consisted of one aqueous solution with a content of 50 g / liter sodium sulfate, 5.0 g / liter sodium bisulfite, 1.0 g boric acid and "I 0.5 g / liter of potassium bromide, together" with the following listed Hesorcin derivatives, where {each one of them was included.

Attempt-
Ki ?. Additional amount (g / liter; no - 1 (control) Resorcinol 5 2 4-chlororesorcinol 5 3 4,6-dichloro-resorcinol 5 4th 4-methoxy resorcinol 5 5 4-methyl resorcinol 5 6 " are in Table VI below The results summarized · Table VI Try Mr. 1 (control) Omkekai density (green density) 2. 1.50 3 2.32 4th 2.42 VJl 2.40 6th 2.35 2.37

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From those listed in Table VI above It is clear from the results that the coupling density can be improved by the application of the anti-fog treatment according to the invention was considerably increased.

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Claims (2)

Claims 1. Phot ο graphic treatment for phot ograr> hi see light sensitive Halogen silver elements, including a preheating and development stage, characterized in that, that one of the photosensitive elements between the pre-curing step and the development step treated in an aqueous solution containing a resorcinol derivative of the general formula contains, wherein A and B each represent a hydrogen atom, one lower alkyl group, a halogen atom, OIL (where R. means lower alkyl group), COR ^ (where Ro is a hydroxyl group, means an alkoxyl group or KHp) or SOpR * (where R-, a hydroxyl group, an alkoxy group or HHvj means) represent. 2. Photographic treatment according to claim 1, characterized in that that the aqueous solution as a resorcinol derivative Resorcinol, 4-chlororesorcinol, 4,6-dichlororesorcinol, 4-methoxyresorcinol, Contains 4-methyl resorcinol or 4-carboxyresorcinol. 909819/10 2 8