DE2104816A1 - Method of hardening gelatin - Google Patents

Description

The invention relates to a method for hardening gelatin. Gelatin is used in the manufacture of elements of many photographic sensitive materials, e.g., silver halide emulsion layers, anti-emulsion layers, filter layers, interlayers, antihalation layers, backing or backing layers, auxiliary layers of backing films or waterproof copier papers, and barite layers of copier papers. Photographic sensitive materials containing such gelatin are often treated with many aqueous solutions having different pH values and temperatures. When the gelatin

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containing layer is not treated with a hardening agent it has poor resistance to water, i.e., containing gelatin The layer swells excessively in water and is easily scratched; this is especially true at high temperature the case in which the gelatin-containing layer is dissolved in an aqueous solution.

A number of compounds have heretofore been known which are useful in increasing the water resistance of the gelatin film is effective by hardening the gelatin. Examples of this are inorganic compounds such as chrome alum, Aldehydes such as formaldehyde, glyoxal and glutaraldehyde and aldehyde derivatives such as chIomuconic acid (mucochloric acid) and 2,3-dihydroxy-1,4-dioxane. They are known as "hardeners", those in the manufacturing stage of the photographic sensitive materials or in the processing stage of these materials are used.

However, these hardeners have some disadvantages when added to photographic sensitive ones Halogen silver materials are used, namely (1) they have an adverse influence on the Properties of the photographic sensitive materials, e.g. increased fogging of the emulsions, Decrease in sensitivity and so-called "post-curing" due to the slowing down of the extent of the reaction for the Harden the gelatin, (2) they lose their hardenability by causing a mutual Reaction with other photographic additives for ordinary use and (3) they are still unsatisfactory with a view to improving mechanical strength, resistance to scratching the gelatin layer, although the water resistance of this increases.

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In addition, the above hardening agents have Disadvantages in that fogging is caused on the photographic emulsion layer does not make the photographic sensitive materials more effective during a processing period Can harden because of the low degree of hardening reaction of gelatin, a bad way Color density is obtained as a result of the mutual reaction with color formers and in the case of hardening in the treatment step when using a curing agent, for example 2,3-dihydroxy-1,4-dioxane (see US Pat. No. 3,330,829 and British Pat. No. 999 145), the pH of the treatment solution is limited to the alkaline range, if this is added to the treatment solutions as a hardening agent in the rapid treatment of the photographic sensitive materials (a process for treatment in a short period of time at high temperature or at high pH) and for treatment, which requires a long period of time, for example, in a treatment for color photographic reversal treatment of photosensitive materials (a process in which the entire treatments, such as first development, color development, interruption, fixation, bleaching and rinsing or the like. during a run for a long time).

An object of the invention is to provide new gelatin hardening agents excellent in water resistance and excellent scratch resistance, which does not, however, adversely affect the Properties of photo ^ raphieclion sensitive materials have, the above-described shortcomings and disadvantages are improved.

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According to the invention a method for hardening gelatin is provided, wherein the gelatin with a new compound of the following general formula (I)

H.

R ^

-OH

(D

Hv

R £ \

is reacted, wherein R ^ and R ^, which can represent the same or different radicals, each a hydrogen atom, an alkyl group, halogen-substituted alkyl group, alkoxyalkyl group, aryl group or aryloxy alkyl group and R-, and R ^, which are the same or different can each represent a hydrogen atom, a methyl or ethyl group with the proviso that the radicals R ^ and Rr do not mean hydrogen atoms at the same time.

^ According to the invention, it is possible to increase the water resistance and to increase the scratch resistance of the gelatin-containing coating layers and molded articles.

Typical compounds for the new curing agents used according to the invention are given below listed .:

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link (D (F; 91 - 93 ⁰ C) JCH C.
H ^ l cr> 3
| ^X 0H ■ ^ C
H "^ ο / C ^
"OH link (2)

^H / I ^CH 5

^ C ^ q / cC ^ (P: 107 - 108 ° C)

-'Link

¹ SiI ί I- £ ^Ε '

(F: 120 - 122Ό)

Connection (4) '- '"■ - '.

η ^. ^ d ^ ^ -cn ce, '. ·

H -, - J * ^ or ^ (F: 89 - .92 ⁰ C)

H- ⁰ ^ O- ^^ s OH-

Connection (5). · · ■

³ ? ? - OH ²

(F: 104 - 107 ^J C)

'Connection (6).

^ O ^ ^ -OH

Ϊ f ^> (F: 92 -

^ ^l '-o-' ^u ^ - CH, ·

Connecting (7)

ClHC ^. - ⁰ ^ ^ - CH

² H- ^ Y - · T ^ OB ⁵ (P: 111-113C) H * * ^ H

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Compound (8) - ■ - CH _x - (CH ₀ ) _lt -CH _o ^ _Λ ^ O ^ "I ^ OH,

^ - _H 3 (F: 98 -

^; * - OH

Connection (9)

CH - (CH ₂ ) ₂ -CH ₂ -0-CH ₂ ^^ / O _n ^ CH

H - C C - H (F: 107 -

Connection. (10)

"- '■■■ u - ^ - *. C -" ^ ^H ( ^{Fi 108} ~

Connection (11)

^{: H} 2 \, J ^0H ( ^{Fi 1} 32 -

The new hardeners used according to the invention have a good hardening effect without the bad influences on the photographic properties of the photographic emulsions (sensitivity j halftone, storage stability and haze or the like) when added to the photographic silver halide emulsions own. In addition, the hardening agents have a characteristic property that they have the Quickly harden gelatine after application as a coating.

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This rapid hardening effect is particularly necessary for the production of photographic sensitive ones Materials with a stable quality without causing "post-cure".

The new hardening agents used according to the invention can be a pre-hardening solution, a treatment bath prior to hardening of the gelatin layer prior to development or a developing solution in a photographic processing method of photographic sensitive ones Halosilver materials are added, with a rapid curing reaction to a sufficient extent without the occurrence of any undesirable photographic Influence on the silver halide, e.g. fogging and adverse mutual reactions with color formers, takes place. The treatment solution containing the compounds according to the invention can have a pH value within have a wide range from 4 to 11, being shows an effective hardening function.

The compounds used according to the invention lose their hardening effect in the presence of others photographic accessories are not. Containing the gelatin Coating layers or moldings produced by the process have been cured according to the invention, have preferred and advantageous properties, in addition to the water resistance but also the mechanical strength, such as scratch resistance (or sliding properties), is remarkable is improved compared with the state before hardening.

The new hardeners used according to the invention can be prepared by reacting \ on 1,2- (or vic.-J-Dohjd vaten with an equimolar amount of Honoalkylglyoxal or 1,2-diketone on phosphorus pentoxide or another Desiccant under reduced pressure or with a

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" i

equimolar amount of monoalkylglyoxal or 1,2-ketone can be made by heating. Some typical synthesis procedures are shown below with reference to the preparation examples explained.

Production example 1

A mixture of 6.2 g of ethylene glycol and 24 g of 3O ^ iger aqueous solution of methylglyoxal was kept under vacuum over phosphorus pentoxide until it was almost solidified. By adding a small amount of ether to the resulting solidified product and filtering it, "20 g of light yellow crystals were obtained. These crude crystals were recrystallized with ethanol,
v / ob on 6.8 g of compound (1), namely 2-methyl-2,3-dihydroxy-1,4-dioxane, which was used according to the invention, was obtained.

Elemental analysis; (CkH-jq

Calculated: C 44.77 %; H 7.46 %

g.ef. : C 44.76 % -, H 7.60 %

The above compounds (2), (4), (5), (6), (8) and (10) were prepared according to the same procedure wisely made.

ü ^v

Manufacturing example 2

9g of 2,3-butanediol and 18g of a 40% aqueous solution of methylglyoxal were mixed. V, ^T ater was using at a solution temperature of 60 to 70 ^ C under a reduced pressure of 30 to 40 mmHg

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a rotary evaporator distilled off. After 3 hours, water had distilled off in an amount corresponding to 95% of the calculated amount. The reaction mixture solidified over phosphorus pentoxide while standing under reduced pressure. After washing with a small amount of acetone, the product was recrystallized twice from ethanol, where 2.7 g of the compound (3), namely 2,5,6-trimethyl-2,3-dihydroxy-1,4-dioxane, with a melting point of 120 to 122 ^° C. were obtained.

Elemental analysis: (CyELrO ^)

calc. ι C 51.85 %; H 8.64 %

found .; C 51.47 %; H 8.86 %

The above-mentioned compounds (7), (9) and (11) were prepared by the same procedure.

The amount of hardening agent used according to the invention is not limited. When added to the gelatin containing coating layers or shaped bodies, however, usually a range of 0.1 to 10 wt .- ^, based on gelatin, preferred. The hardening agents can be used alone or in the form of a mixture two or more of these can be used, or they can be used together with other known hardening agents come into use.

In the case of using the compounds according to the invention in a pre-hardening treatment of photographic delicate halo-egg silver materials will, although the concentration of these compounds on the type of photographic materials, the composition of a

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Depending on the pre-hardening solution and the subsequent treatment stage, a range from about 1 to 50 g / l preferably used. The pre-hardening solution can be sodium sulfate, water softener, potassium bromide, or a contain other antifoggants and, in addition to the compounds mentioned, a buffer salt. . The pH of the solution can be within a wide range from 4 to 11, but with a pH of 4.8 in terms of photqgrap properties and the strength of the emulsion film is appropriate.

When used together with formaldehyde in the

In the pre-curing solution, a high curing effect can be obtained by adding 5 to 30 ml of a 37% aqueous formaldehyde solution to 1 liter of the pre-curing solution in addition to the compound according to the invention in the range specified above.

When developing the photographic sensitive materials by adding a Hardening agent according to the invention is hardened to a developer solution with development, is the optimal one Concentration of hardener in the range of from about 1 to 20 g / l, albeit that of the composition | the developer solution and in particular on the concentration of sulfite ions depends. In the case of the encore the gelatin emulsion layer is not only strongly hardened but becomes a color developing solution also caused only slight fogging and a disadvantageous mutual reaction with the / color former Hardly appears to the same extent as in the case of adding to the pre-hardening solution away.

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ff

When the method according to the invention is applied to the photographic sensitive materials various silver salts, such as silver chloride, silver bromide, silver iodide and mixed silver halides, such as silver chlorobromide, silver iodobromide and silver chloroiodobromide, for Application. In addition, the photographic sensitive materials can be used Additives such as chemical sensitizers, optical Sensitizers, antifoggants, coating aids, stabilizers, plasticizers and development accelerators contain.

The hardening agents according to the invention are not only used in the photographic sensitive materials but also for hardening layers containing gelatin, for example color filters and baryta paper and gelatin containing molded bodies, e.g., gelatin capsules and gelatin plates or sheets.

The invention is explained in more detail below with reference to examples.

example 1

Samples were made into an aqueous gelatin solution by adding Compounds (8) and (10) according to the invention with a content of 50 g gelatine per 1000 g solution in the size indicated in Table I below and uniformly applying to one having an auxiliary layer provided cellulose triacetate film base for the formation of a dry film with a thickness of 10 / U and drying.

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After aging the resulting samples for 1, 5 and 14 days at room temperature and under accelerating aging conditions for 2 days, the temperature at which the gelatin films melt was in a 2% aqueous solution of Na ₂ CO,. K ^ O determined, the temperature of which increased by an amount of 1 ⁰ C per min v / urde (this temperature was given below as the melting point). The samples aged under accelerating conditions were subjected to a determination of the scratch resistance in the dry state or after immersion in a 2% strength aqueous solution of Na _{2 CO, .HpO for 10 min}

^ subject. The strain that is on the gelatin films A scratch revealed by means of a needle was determined by holding the pen with a diamond ball with a Radius of 0.05 mm at its tip in the former case and with a stainless steel ball with a radius of 0.8 mm at its tip in the latter case drawn perpendicular to the surface of the gelatin films and the needle parallel was moved on the surface of the gelatin film by an amount of 5 mm per second (hereinafter the load of the pen that resulted in scratching a dry gelatin film is referred to as dry scratch resistance and the stress of the pen on the gelatin film after immersion in the alkali aqueous solution

ψ referred to as wet scratch resistance).

The results are summarized in Table I below.

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Table I.

link

Amount of melting point of the Ge (mol / kg) latine film ( ⁰ G) room temperature

1 day 5 days 14 days

accelerate.
Aging
80% relative humidity
, 2 days

Scratch resistance dry wet

to σ co co

no (control) connection (8)

2x10 '

0 '

-3, -3

ConnectiondO) 2x10 "" ³

4x10 '

-3

35

35

35

38 40 40 42 45 45 40 42 42 44 48 • 48

25th

13th

30th 42 33 65 38 92 45 100

From the results in Table I above, it can be clearly seen that the samples with an additive of compounds according to the invention have a high melting point and a high scratch resistance of the gelatin film compared to the samples that did not contain any additive. The hardening reaction was rapid and sufficient to a point near the maximum melting temperature by standing for 1 day or 5 days at room temperature.

Example 2

Samples were prepared by applying an aqueous solution containing 80 g of gelatin per 1 kg of the solution to a polyethylene terephthalate film support provided with an auxiliary layer in such a way that a dry coating film with a thickness of 10 / rev was obtained after drying. After immersing the resulting samples in aqueous solutions containing 5 g of the compound (7) or the compound (9) according to the invention for 1 minute, the melting point of the gelatin film, the wet scratch resistance and the dry scratch resistance were determined. The determination of the melting point of the gelatin film and the wet scratch resistance were carried out in a 2% aqueous solution of NapCO ^ .HpO without drying the sample in the aforementioned aqueous solution. The dry scratch resistance was determined after drying at room temperature after immersing the samples in the manner described above. The results are shown in Table II below.

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35
60
64 Scratch resistance wet Table II dry 13th
32
40 Compound melting point ( ⁰ C) 25th
35
38 no control)
Connection (7)
Connection (9)

From the results of Table II above it can be seen that samples treated with the aqueous, Compounds according to the invention containing solution exhibited a higher melting point and higher scratch resistance than a sample made with a Solution which did not contain any of these compounds was treated.

Example 3

Samples were prepared using the compounds (1), (2) and (3) according to the invention and a well-known additive of methylglyoxal sodium bisulfite to photographic emulsions containing 70 g of gelatin and 60 g of silver bromide per 1 kg in the in the amounts shown in Table III below were respectively added and the emulsions were uniformly coated on a cellulose triacetate film base provided with an auxiliary layer so as to obtain a dry coating film having a thickness of 10 ax , followed by drying.

After application, the samples were kept at room temperature for 3 days, 7 days, 14 days and 28 days, respectively ditched. Then the melting point of the emulsion layers of the samples was determined, the samples being in a 2% aqueous solution of KapCO ^ .EpO were immersed,

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The results are shown in Table III below listed.

V been allowed to stand at room temperature after the application of long the Ilaßkratzfestigkeit of the samples, the 30 day / arene was determined min by immersion in a 2 $ strength aqueous solution of "Napco ^ .HgO at 20 ⁰ C for 10 The results are in. Table IV below.

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Table IiI

Sample no »connection

Amount of melting point of the emulsion film ( ⁰ C) (mol / kg), storage at room temperature - for 3 days 7 days 14 days 28 days

1
2

3
4th

no control)

Addition product

Methylglyoxal

sodium bisulfite

Connection (1)

Connection (2)

Connection (3) 35

35

35

35

4x1 Cf ³ 6x1Cf " ³ 4x1 Cf ³ 6x1 Cf ³ 4x1 CT ³ 6x10 ~ ³ 4x1O ^-3 6x1 Cf ³

41 41 41 41 42 42 42 42 41 41 41 41 46 46 46 46 51 52 52 52 63 63 63 63 42 42 42 42 52 52 52 52

The photographic properties of samples aged for 30 days at room temperature was developed by 2CFG after developing with a developing solution having the following composition determined during 10 min fixing, rinsing and drying, and the results are given in Table IV below.

Composition of developer solution;

N-methyl-p-aminophenol sulfate 1.0 g

Sodium sulfite (anhydrous) 75.0 g

Hydroquinone 9.0 g

Sodium carbonate monohydrate 30.0 g

Potassium bromide 5.0 g

Water rest to 1 1

Table IV

Sample wet scratch (relative Smpfind no. Resistance (fog +

speed (g) optical concentration
0.1)

100 78 75 91 f 5 42 80

, 85 80 36 80

1 17th 2 17th 3 17th 4th 32 5 42 6th 60 7th 100 8th 42 9 60

gamma veil 1.86 0.07 2.11 0.08 2.02 0.08 2.10 0.05 1.94 0.04 1.96 0.06 1.86 0.04 2.00 0.05 1.90 0.05

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It is clear from the above results that the samples with the compounds according to the invention had a high melting point and that the compounds according to the invention less exerted undesirable effects on photographic properties compared to the known hardening compounds. In addition, it was scratch resistance remarkably increased.

Example 4

Samples with a film thickness of 10yu were made, wherein the compound (3) and (4) and (5) and a known addition product methylglyoxal sodium bisulfite in the amount given in Table V below, in each case see the photographic emulsions with a content of 75 g gelatin and 62 g iodobromide silver (iodine content 5 MoI-Jo) were added and the emulsions uniformly and homogeneously on a cellulose triacetate film base provided with an auxiliary layer applied and dried.

After the application of each sample at 50 ⁰ C, 80? Srelativer humidity for 2 days was allowed to stand and the increase amount of the thickness of the layer was During by immersion in v / ater at 10 2 CFC determined min.

The photographic properties of the same sample were determined by development using a Developer solution with the introductory described in Example 3 Composition determined. The results are shown in Table V below.

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Ilabelle V

Sample connection no .:

Amount (mol / kg) Increases in relative gamma haze measured thickness sensitivity

OQ

1 2

3 4 5 6 7 8 9

no control) (

Addition product methylglyoxal sodium bisulf it 4x10 "

»6x1 θ"

Connection (3) 4x10

Connection (4)

Compound (5) η

6x1 O * " ³ 4x10 ~ ⁵ 6x10"" ⁵ 4x10 ~ ⁵ 6x10 ~ ⁵ 380

370
370
330
330
320
280
320
310

100

83 76 92 89 89 85 93 91

1.60

0.14

1.65 0.13 1.54 0.13 1.56 0.08 1.54 0.07 1.58 0.06 1.55 0.06 1.58 0.07 1.56 0.08

From the results in Table V above, it is clear that a deteriorating effect of the See compounds according to the invention on the photograph! Properties in the iodobromide silver emulsion compared to known compounds is also very low. It can also be seen from the increase in the thickness of the layer that the degree of hardening of the layer was improved.

Example 5

Samples with a film thickness of 10 / u were prepared, by the compounds (1), (3) and (5) according to the invention and ChIοmuconsäure as a known hardener compound in the in the following table VI indicated the amount of each photographic emulsions with a content of 75 g Gelatine and 70 g of chlorobromide silver (bromine content 40 mol%) 1 kg each were incorporated and the emulsions were uniformly applied to a small extent with an auxiliary layer provided (small subbed) cellulose triacetate film backing were applied and dried.

After application, each sample was aged for 3 days, 7 days and 30 days at room temperature, respectively, and the The melting point of the emulsion layer became the same Procedure as indicated in Example 1, determined. The results are shown in Table VI below.

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Table VI

Sample no .: link lot (Mol / kg) 1 no control) 0 2 Chloromuconic acid 2x10 "" ³ 3 ti 4x10 " ³ 4th Connection (1) 2x10 ~ ³ 5 ti 4x10 " ³ ro 6th Connection (1) 2x10 "" ³ ο + Chiο rmucon- _ co acid 2x10 "' 00 7th Connection (3) 2x10 " ³ O 8th ti 4x10 "" ³ - » 9 Connection (3) 2x10 "° O)
£ '"% + Chlormucone CD
NJ acid 2x10 "^ 10 Connection (5) 2x10 "" ³ 11 Connection (5) 2x10 " ³ 12th Connection (5) 2x10 ~ ³ + Chlormucone acid 2x10 "°

Melting point of the emulsion layer ( ⁰ C), storage at room temperature for days 7 days 14 days 30 days

35 35 35 35 37 39 41 41 39 43 45 50 39 41 41 41 43 43 43 43 61 63 63 63 42 42 42 42 45 46 46 46

65

39
44

62

65

42
44

42 44

65

42 44

63

From the above results it can be seen that the emulsion layers are also without Prevention of the curing effect of each curing agent when used together with another curing agent.

Example 6

A red-sensitive silver bromide gelatin emulsion layer containing a cyan coupler, a gelatin layer containing a hydroquinone derivative for preventing parboid contamination, a green-sensitive layer silver iodobromide gelatin emulsion layer containing a magenta coupler, a yellow filter layer containing colloidal silver iodine particles -Layer containing a yellow coupler and a surface protective layer containing gelatin were successively applied as a coating or overlay to a triacetyl cellulose film base provided with an auxiliary layer and dried. The reversal color film of high sensitivity thus prepared was exposed to light and treated after the following treatment steps.

Treatment stage Temperature ( ⁰ G) Duration (min) Hardening bath 30 1

Rinse ^w ' ⁿ

first development ^w 3

Rinse "0.5

Reversal exposure (uniform exposure of 8000 lux / sec

on the emulsion surface)

second development; 30 4

Rinsing «1

LEADS ««

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- Sä -
Zh ( ^C C) 210A VJl 816 Duration (rain) temperature O,
1
It 30th
Il
Il

Treatment ^ level Rinsing Fixing Rinsing

The composition of the respective treatment solution is given below:

Composition of the hardening solution

Sulfuric acid (specific weight: 1.84) water sodium sulfate sodium acetate Formalin (37% aqueous solution)

Hardener amount as in after

Table VII below (optimal amount)

2 , 7 ml 2 , 7 ml 150 δ 20th G 10 ml

water rest on 2.0 1 ß 90.0 G Composition of the first decoiling solution: 8.0 G N-methyl-p-aminophenol sulfate 52.5 G Sodium sulfite 5.0 G Hydroquinone 1.0 G Sodium carbonate (monohydrate) 1 1 Potassium bromide Potassium thiocyanate Water rest on

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is

Composition of the second developer solution:

Benzyl alcohol 5.0 3-methyl-4-amino-N-ethyl-N-methanesulfone-- 1.5 ml Sodium sulfite 5.0 amidoethylaniline sulfate 1.0 Hydroxylamine hydrochlorate 2.0 Potassium bromide 30.0 G Sodium pho sphat 0.5 Sodium hydroxide 7.0 G Ethylenediamine (70% aqueous solution) 1 G Water rest on G Composition of the bleach solution: 100 G Ferricyanide 40 ml Sodium acetate. 20th 1 Glacial acetic acid 30th Potassium bromide 1 G Water rest on G Composition of the fixing solution: ml G 1

Sodium thiosulfate 150 g

Sodium acetate 70 g

Sodium sulfite 10 g

Potassium alum 20 g

Water rest to 1 1

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In the standard treatment method described above, the known compound 2,3-Dihydroxy-1,4-dioxane and glutaraldehyde as / ie die Compounds 1 and 3 according to the invention of the hardening solution in the table VII below Amount added. After the treatment, the photographic properties were determined. Besides became the state of destruction of the emulsion layer during the above photographic processing (which is shown in the table below as "Degree of Occurrence of Wrinkles").

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Table VII

Sample no. Hardening agent,

Photographic behavior

... ,, "". "^ I ^^^^^^ niaxiinal concentration density of the trans solution together with tration parent part formula m (g / l) tpaint spots)

1 no (control) R. _G _J5 2 Compound (1.) 17.4 2.59 3.09 2.86 3
4th Compound (3) 21.1
2,3-dihydroxy-1,4-
dioxane 1 β, 4 3.24 3.55 3.18 2098 25 ^ ige aqueous
Solution of
Glutaraldehyde 3.5 3.12
2.71 3.43
3.30 3.07
2.98 110/1 annotation : R, G and B mean 2.96 3.15 2.87 602 respectively the through one

0.16 0.16 0.13

0.14 0.13 0.10

0.14 0.13 0.10

0.15 0.13 0.11

0.15 0.14 0.11

Degree of occurrence of wrinkling

bad

Well

Well

a little worse a little worse

certain color density.

It is clear from the results in the table above that the treatment was possible practical to perform at high temperature, since crosslinking occurs due to the increase in Strength of the emulsion layer was not observed, and that the extraction of images of excellent Quality was made possible when the samples were used, dfe a previous treatment with a hardening agent solution containing the compound according to the invention (samples 2 and 3) compared to the sample that was treated with a hardener solution that did not contain this compound, (Standard treatment) (Sample No. 1) and compared to the samples subjected to treatment with a Hardening agent solution containing the known compounds (samples Nos. 4 and 5).

After sufficient rinsing of each of the above samples, the temperature at which the emulsion layer was destroyed when was heated in a 0.2 η aqueous solution of sodium hydroxide, determined (this value below is specified as the wrinkle grain formation point). The results are shown in Table VIII below compiled; it can be seen that samples subjected to treatment with a compound according to the Invention containing hardener solution had been subjected (sample Nos. 2 and 3), a have higher wrinkle point than the comparative samples (Samples Nos. 1, 4 and 5). From these results the effect of the compound according to the invention on emulsion film strength can be clearly seen.

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Table VIII

Sample no .: added hardening
middle Wrinkle grain
educational
point ( ⁰ C) 1 no (control) 43.0 2 Connection (1) 50.5 3 Connection (3) 49.0 4th 2,3-dihydroxy-1,4-
dioxane '47.5 5 Glutaraldehyde 46.5 Example 7

A positive photographic, sensitive one Material obtained by applying a chlorobromide silver emulsion containing 75 g of gelatin per 1 kg the emulsion on one provided with an auxiliary layer Cellulose triacetate film base was exposed and treated as follows.

Treatment stage 'Treatment temperature Treatment ( ⁰ G) duration (min)

Development 35 2

Fix "1.5

Rinse »1.5

The compositions of the developer solutions used are given below.

A commercially available acidic hardening fixing solution was used for fixing.

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- BQ - 2104816 Λ G Tß Composition of the developer solution: xi
4.5 G 4.5 g N-methyl-p-aminophenol sulfate 15.0 G 15.0 g Sodium sulfite 8.0 G 8.0 g Hydroquinone 41.0 G 41.0 g Sodium carbonate monohydrate) 3.0 G 3.0 g Potassium bromide 0.1 0.1 g 6-nitrobenzimidazole - G 8.7 g Compound (1) according to the invention 0.5 G 0.5 g Sodium anthraquinone sulfonate 0.1 G 0.1 g Sodium hydroxide 40.0 1 40.0 g Sodium sulfate 1 Water rest on

A great difference in photographic properties was found using the developing solution A or the developer solution B was not observed. However, the points were the wrinkling of the emulsion layer different as this from the following. Table IX can be seen and an excellent V-ilialt ^ r against a high-temperature treatment was found when using the developing solution B containing the compound according to the invention became.

. Table IX

Treatment solution Wrinkle grain formation point __ of the emulsion film

A. 35 ⁰ C

B 43 ⁰ C

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- SG -

Example 8

A sensitive reversal color material which, by applying a red-sensitive iodobromide silver gelatin emulsion layer, a green-sensitive silver iodobromide gelatin emulsion layer; a yellow filter layer containing colloidal silver particles and a blue-sensitive silver iodobromide gelatin emulsion layer in the specified order onto one provided with an auxiliary layer Triacetyl cellulose film base and drying was exposed and then in the treated in the following manner:

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Treatment; s level Duration (min)

1. Hardening bath i

2nd rinse 2

3. Negative development 4

4. Rinse 3

5. Reversal red flash exposure

6. Cyan color development. 4th

7. Rinse 3

8. Reversal blue flash exposure

9. Yellow color development 4

10. Rinse 3

11. Reversal white exposure

12. Magenta color development 4

13. Rinse 3

14.Silver bleaching 3 15 · Fixing 3 16. Rinsing 3

The temperature of each of the above treatment solutions was 27 ^° C. and their compositions were as follows:

First developer solution:

N-methyl-p-aminophenol sulfate 2.0 g

anhydrous sodium sulfate 90 g

Hydroquinone 8.0 g

Sodium carbonate (monohydrate) 52.5 g Potassium thiocyanate 1.0 g

Water ■ rest to 1

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- 3ft -

Cyan color developing solution:

anhydrous sodium sulfite 5.0 g

4-Amino-3-methyl-N, N-diethylaniline hydrochlorate Sodium carbonate (monohydrate) Potassium bromide Potassium iodide (0.1-6 aqueous solution) 1,5-dihydroxy-2,6-dibromonaphthalene Sodium hydroxide

Water rest on

Yellow color developer solution :

anhydrous sodium sulfite 4-amino-N, N-diethylaniline sulfate Potassium bromide Potassium iodide (0.1% aqueous solution)

CO -Benzene-4- (p-toluenesulfonamide) -acetanilide

Sodium hydroxide

Water rest on

Magenta color developer solution:

anhydrous sodium sulfite 4-amino-3-methyl-N, N-diethylaniline sulfate Potassium bromide 1-phenyl-3- (m-nitrobenzoylamine) -5-pyrazolone Sodium hydroxide n-butylamine

Water rest on

Bleach solution;

Ferricyanide Potassium Bromide Borax

Boric acid

Water rest on

209810/1602

ο, , 6 G ml 15, , 0 G G O ₁ , 25 g G 2 1 1, , 2 G 2, , 0 G 1 G 5, 0 ml 2, 5 G 1, 0 G Ul 1 1, 2 G 2, 5 G 1 G 5, 0 G 2, 0 G 0, 2 ml 1, 4th 1 2, Ul G 5 G 1 G 100 G 10 1 2, 0 1, 0 1

3H

Fixing solution ;

Sodium thi ο sulfate

anhydrous sodium sulfate

water

Pre-hardening solution ·! Approach A sodium hexamethapho sphat
Sodium bisulfite

Sodium pyrophosphate (10 hydrate)
Sodium sulfate
Potassium bromide
W. Sodium hydroxide

37/4 aqueous formaldehyde solution Water E.

Pre-hardening solution / g ;; Approach B

17.4 g of the compound (1) according to the invention werden.zu Addition A above.

Pre-hardening solution; Approach C

21.2 g of the compound (3) according to the invention are added to batch A above.

Pre-hardening solution; Approach D

6.8 ml of a 25% aqueous glutaraldehyde solution are used added to batch A above.

Pre-hardening university: slösunr? ;; Approach Ξ

16.4 g of 2,3-dihydroxy-1,4-dioxane added value to the above Approach Λ added

150 g G 10.g G Rest on 1 1 G 2.0 G 5.0 G 15.0 G 150.0 ml 2.0 1 0.1 ng 15th t on 1

209810/1602

-54- 21CH816

The photographic properties and the Runzelkornbildungspunkt of each P _r obe, the photographic processing obtained in the above-described ^ were determined; the results obtained are shown in the table below.

209810/1602

Table X

Prehardening Photographic Behavior Wrinkle Grain Mildungspunkt

^solutions maximum con-. Reverse of ^the emulsion layer (° C)

centering sensitivity

R G B R G B

J £ A 36.0 3.00 3.15 100 100 100 43,

ο vif

3.83 3.22 3.31 '95 95 95 50 ₍

3.75 3.20 3.25 97 97 100 48

3.25 2.73 2.70 125 140 140 48

3.70 3.10 3.18 97 98 100 45

From the table above it can be clearly seen that a sufficient maximum concentration and a satisfactory reversal sensitivity was obtained in the samples that were subjected to the treatment with the precuring solution containing the compound according to the invention (B and C). When the treated film sample is heated in a 0.2 N aqueous solution of sodium hydroxide, the temperature is at which the soot grain formation takes place is sufficiently high, and the film sample has a sufficient one Strength to a development by means of an automatic developing apparatus through which mechanical scratches are easily caused to harden.

In contrast, the maximum concentration and strength of the emulsion layer are in the samples which have been subjected to treatment with a pre-curing solution (A) other than formaldehyde contained no hardener. In addition, the samples that are subject to treatment with a pre-hardening solution with a content of glutaraldehyde (D) and a pre-hardening solution containing 2,3-dihydroxy-1,4-dioxane (E), the photographic properties deteriorated although the strength of the emulsion layer is high or, on the other hand, the strength of the emulsion layer is low, although the photographic properties are not deteriorated. In any case, these materials are for the not suitable for practical use.

209810/1602

Claims (10)

Claims Process for hardening gelatin, characterized in that the gelatin is made by using a compound of the general formula below »3 hardens, v / orin R ₁ and Rp »can represent the same or different radicals, each a fiber atom, an alkyl group, a halogen-substituted alkyl group, alkoxyalkyl group, aryl group or aryloxyalkyl group ^ and R ^ and R ^, which can be the same or different , each represent a hydrogen atom, a methyl or ethyl group, with the proviso that the radicals R ^ and R ^ do not represent hydrogen atoms together at the same time. 2) Method according to claim 1, characterized in that that the gelatin to be hardened as a layer of a photographic, light-sensitive silver halide material is present. 3) Method according to claim 1, characterized in that that the gelatin to be hardened is in the form of an aqueous solution. 209810/1602 4) Method according to claim 1, characterized in that that the compound of the general formula given is in the form of an aqueous solution used. 5) Method according to one of claims 1 to 4, characterized in that there is used as a compound of the specified general formula one of the compounds given below is used: Connection (1) ° \ ^% | ^N 0H * (F; 91-93 ⁰ C) _Q / ^N OH Connection (2) 3tt - * - C C · - ü I I ^un 3 g ^ CvQ ^ cCg ³ (F: 107 - 108 = C) - "connection (3) H "" * "^ *" ^ * "~~ CE ⁵ H- ^ '' ^ H ³ (F: 120 - 122 ³ C) Connection (4) ' H ^ _C ^ 6 ^. ^ - CK CH, ι ι _C CK CH, ^a "^ * ι ι ^ * ^0K (F: H - ^; ^{c <s} - o- V ^ * OE connection (5) f ^ OH ² r ^ -H '(F: 0981 ff? 1SD2 HO 'Connection (6). OH
CK ^0Η if , ^ CK ₃ / _{F. 9} 2 - Connection. (7) O _CK -? <0H ⁵ '(F: 111 - 11? C) Connection (8) ■ - · . · ■ ". '. H ^ r ^ or ⁰ " ~ * oh Connection (9)
- CH - (CHJ-CH-O-CH ^ / 0-. CH, H -— C C-H (F: 107 - Connection (IO) ? ^ - 0H ,! - H (P: 108 - ^C - OH Connection (11) H _{(F: 132} _ H ^^ ^{ü X} 209810/1602 Vf 6) method of hardening a gelatin-containing layer of photographic materials, characterized in that the layer is treated with a compound of the general formula below treated, wherein R-, and R ₂ , the same or different radicals, each a hydrogen atom, an alkyl group, an alkyl group substituted with halogen, an alkoxyalkyl group, an aryl group or aryloxyalkvlgruppe and R- * and R ^, which are the same or different can be, each represent a hydrogen atom, a methyl or ethyl group, with the proviso that R ^ and R ^ do not represent hydrogen atoms together at the same time. 7) Method according to claim 6, characterized in that that the treatment solution is a pre-hardening solution is. 8) Method according to claim 6, characterized in that the treatment solution is a developer solution is. 9) Photographic gelatin-calogensilver emulsion, characterized in that it is a compound the general formula below 209810/1602 BAD ORKSlNAt St. "210A816 . OH rx / 4 contains, wherein R ,, and Rp, which can be the same or different radicals, each a hydrogen atom, an alkyl group, an alkyl group substituted by halogen, alkoxyalkyl group, aryl or aryloxyalkyl group and R ₇ and R, which can be identical or different , each represent a hydrogen atom, a methyl or ethyl group ™ with the proviso that R- * and R ^ do not mean hydrogen atoms together at the same time. 10) Color photographic material with one 'Carrier and a light-sensitive gelatin-PIalogen sirber emulsion layer thereon, characterized that the photosensitive gelatin-halogen silver-SinusLonsschicht a color-forming coupler and a compound represented by the general formula below \ s ^0H contains, wherein R-] and Rp, the same or different Can be residues, each a ".vasserctoffatom, an alkyl group, an alkyl group substituted by halogen, alkoxyalkyl group, Aryl group or aryloxyalkyl group and R and R ^ / which can be the same or different, each represent a hydrogen atom, a methyl or ethyl group with the proviso that R, and R ^ are not at the same time together mean hydrogen atoms. 209810/1602 - ■ ι BAD OFFICIAL