DE2240982A1 - METHOD OF FAST CURING GELATINE - Google Patents

Description

DR. E. WIEGAND DIPL-ING. W. NIEMANN ^ ^

DR. M. KÖHLER DIPL-ING. C GERNHARDT

MÖNCHEN HAMBURG

TELEPHONE: 555476 8000 MDNCHEN 15,

TELEGRAMMER CARPATENT 'NUSSBAUMSTRASSE 1.0

August 21, 1972 W 41 282/72

Fuji Photo Film Co., Ltd. Minami Ashigara-Shi _% Kanagawa (Japan)

Process for the rapid hardening of gelatin

The invention relates to a method for rapid hardening of Gelatin, ■

Gelatin is used in the manufacture of photographic light-sensitive materials, for example as a binder for the silver halide emulsion, a protective colloid layer, an intermediate layer, a top layer for the film base, an antihalation layer, a layer on the back (Backing layer) etc. A photosensitive material that has some of these gelatin-containing layers, is after exposure under various conditions with developing liquids the most diverse composition treated or developed. When the layers containing gelatin the photographic material is not treated with a hardener during the treatment or development described above, they have poor resistance to water and they swell during treatment or «. Development excessively

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strong and there is a risk that they will be destroyed or damaged. Occasionally the gelatin dissolves a high temperature development of the support. This increases the usefulness of the photosensitive Material severely impaired. Various types of gelatin hardeners have now been used to eliminate these disadvantages of gelatin.

Well-known gelatin hardeners are inorganic compounds such as chrome alum, or organic compounds such as aldehyde compounds, active vinyl compounds and ethylene imino compounds. These hardeners can «depending on the intended use of the Emulsion or the treatment liquid or developer liquid can be added.

However, some of these hardeners have a very long reaction time required to harden the gelatin sufficiently to achieve the desired physical properties (e.g. the desired water resistance and mechanical strength, such as the desired abrasion resistance, etc. photographic gelatin layer) and the desired photographic properties (e.g. the desired density, maximum Density, etc.) in the light-sensitive material is required for a very long time. It has also already been pointed out that the photographic gelatin layer applied to a support is irradiated with high-frequency radiation can be used to dry them. Although it is possible after this method, the gelatin layer within a short time Time to dry, however, this method has the major disadvantage that it adversely affects the hardening of the gelatin.

After extensive investigations, the solution to these problems described below has now been found.

The invention relates to a method for rapid hardening

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of gelatin, which is characterized in that one Support, for example a synthetic resin film, glass or paper, coated with an aqueous gelatin solution which at least one halogen-substituted diazine compound, one halogen-substituted triazine compound, a compound with an active vinyl group, a mucohalogenic acid or a derivative thereof and / or a substituted or unsubstituted 2,3-dihydroxy-1,4-dioxane, and after drying with a constant "speed for a certain period of time this irradiated with high-frequency microwaves.

Examples of suitable halogenated diazine and triazine compounds which can be used as hardeners in the process of the invention are those as described, for example, in US Patents 2,983,611, 3,325,287 and 3,549 and in British Patents 1,072,008 and 1 193 are described, e.g. ^: B. 4-Chloro-2,6-bis (methylsulfonyl) -1,3-diazine, 4-chloro-2-ethylsulfonyl-6-methyl-1,3-diazine, 2,4-dibromo-6-methylsulfonyl 1,3-diazine, 2,4-, 5-tribromo-6-methylsulfonyi-1,3-diazine, 4,5-dichloro-6-methyl-2-phenylsulfonyl-1,3-diazine, 2,3 -Dichlorquinoxaline-6-carboxylic acid chloride, 2,3-dichloroquinoxaline-6-chloro-7-sulfonic acid chloride, N, N-bis (hydroxyethyl) aminodichlorotriazine, the sodium salt of 2,4-dichloro-6-oxy-s-triazine or 2 , 4-bis (1-aziridinyl) -6-chloro-1,3i5-triazine and the like.

Examples of compounds having an active vinyl group that can be used in accordance with the invention may be used are those disclosed in U.S. Patents 3,490,911 and 3,539,644, as well as in US Pat British patent specification 994 869, e.g. Methylenebisacrylamide, 1,2-bis- (2-vinylsulfonylmethoxy) ethane or bis- (2-vinylsulfonylethyl) ether and the like.

Examples of suitable mucohalic acids and their derivatives are those described in U.S. Patents 2,080,019 and 3,579

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and in Belgian patent 725 964 are described, such as, for example, mucochloric acid, mucobromic acid, 3-bromo-2-phenoxymalealdehyde acid, 3-chloro-2-phenoxymalaldehyde acid, 2- (p-carboxyphenoxy) -3-chloromaldehyde acid, 2- (p-methoxyphenoxy) ) -3-chloromaldehydic acid, 2- (p-tert-pentylphenoxy -) -3-chloromaldehydic acid, 2- (p-octylphenoxy) -3-chloromaldehydic acid, 2- (m-pentadecyl) -3-chloromaldehydic acid or 3-GHLOT- 2-phenylthiomaldehydic acid and the like »

Examples of suitable substituted and unsubstituted 2,3-dihydroxy-1,4-dioxanes are such compounds as they U.S. Patent 2,870,013; British Patent 1,270,578 (corresponding to U.S. Patent Application No. 201 999) and in German Offenlegungsschrift 2,104,816 corresponding to US patent application No. 112,014 are, such as 2,3-dihydroxy-1,4-dicocan, 5-chloromethyl-2,3-dihydroxy-1,4-dioxane, 5-phenoxymethyl-2,3 ^ dihydroxy-1,4-dioxane, 2-methyl-2,3-dihydroxy-1,4-dioxane, 2,5,6-trimethyl-2,3-dihydroxy-1,4-dioxane and the like

The amount of these hardeners added depends on the hardening effects achieved therewith, but it is generally within. in the range from 1 to 300 mg per g of dried gelatin, preferably from 1 to 100 mg per g of dried gelatin.

The aqueous gelatin solutions to which the present invention Applicable include gelatin solutions, acetylated gelatin solutions, and succinated gelatin solutions as well as, for example, coating solutions for silver halide emulsion layers, Protective colloid layers, intermediate layers, top layers for film carriers, antihalation layers and backing layers (Layers on the back). These layers of the photographic light-sensitive material contain gelatin and the invention is also applicable to gelatin solutions for

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Encapsulation of microcapsules and the like. These and other gelatin derivatives are in U.S. Patents 2,518,666, 2,525,753 ' and 2,614,928.

In applying the invention to a photographic light-sensitive material having layers containing gelatin the photographic gelatin layers can have various additives, such as coating aids, antifoggants, chemical sensitizers, spectral sensitizers, plasticizers, such as glycerine, dicarboxylic acid esters, such as those in the U.S. Patent 2,940,854- lower alkyl esters of ethylene bisglycolic acid as described in US Pat. No. 2,904,434, couplers, swelling control agents, as described, for example, in US Defensive Publication T 873, and antistatic agents.

As used herein, "drying with a constant." Speed for a certain period of time "means the following: when a carrier with an aqueous gelatin solution is coated and dried at constant temperature and humidity, the water content becomes during the drying process initially reduced proportionally to the time and the rate of decrease of the water content increases then gradually decrease; the first stage of drying is called "drying at constant speed for a certain time " In this case, when the temperature and humidity conditions are varied, only the speed varies the decrease in water content according to each condition during drying at a constant rate for a certain time,

Irradiation with high-frequency microwaves can be carried out at constant speed after drying. willia and the application of a high frequency electric field according to.

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Completion of the drying gives good results without the effects according to the invention being lost. A suitable one Frequency that can be used is one within the IMS bands with frequencies of 13.56 MHz, 27.12 MHz, 40.68 MHz, 915 MHz, 24.50 MHz, 58.50 MHz, 10,600 MHz and 18,000 MHz. The application of frequencies of 2450 MHz and 915 MHz was made recognized by various government agencies for industry as being suitable for achieving the effects of the invention. The time of irradiation with the high-frequency microwaves, which vary depending on the strength of the high-frequency electric field is preferably 1 second to 20 minutes.

According to the invention, the hardening reaction of the gelatin is promoted while reducing the reaction time, so that the physical und'photographic properties of the light-sensitive photographic Material with gelatin-containing layers are constant, resulting in improved performance of the material with great advantages.

The invention is illustrated in more detail by the following examples, without, however, being restricted thereto. The ones specified therein Unless otherwise stated, parts and percentages are based on weight.

example 1

A gelatin-silver iodide emulsion (containing 0.3 mol of silver halide per kg of emulsion) was produced in which the gelatin content was adjusted to 5% and contained the silver bromide particles which had previously been sensitized to gold and sulfur (silver iodide content = 5 Uol- %). The following compounds (1) to (4) were then added to the emulsion in the following amounts:

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Compound (1) (antifoggant) "(2) (optical sensitizer) "(3) (coupler)

(Coating aid) 0.5

1 _S 5 mg 1.5 mg 0.2 mg

Link (

CH.

OH

Connection (2)

CH-C = CH

C ₂ H, SCN

Connection (3)

OCH ₂ COEH

CONH-C CH,

Cl I Cl

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Connection (4)

In addition, 3 mg of the sodium salt of 2-0xy-4,6-dichloro-> s-triazine were added as a hardener per gram of dried gelatin and a wet Kolßntemperatur dried 24 ⁰ C, and immediately after completion of drying at constant temperature according to the following steps (a) to (g) dried and stored (in this test, the water content of the coating layer was 30%) to form the following samples (ft) to (g);

(a) storage at 25 ⁰ C and 45% reltiver humidity (HH);

(b) Irradiation with a high-frequency electric field for 30 seconds (to minimize the problems caused by the electric wave, the same conditions, 2450 MHz, 5 ^ W, were subsequently applied) and then at 25 ^° C and 45% HH stored?

(c) Storage at 25 ^° C. and 45 % EH after irradiation with a high-frequency electric field for a period of 1 minute;

(d) storage at 25 ° C and 45 % EH after irradiation with a high frequency electric field for a period of 2 minutes;

(e) Storage at 25 ^° C. and 45 % EH after irradiation with a high-frequency electric field for a period of 5 minutes;

(f) Storage at 2 5 ^° C. and 45 % BH after irradiation with a high-frequency electric field for a period of 20 minutes;

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(g) Immediate irradiation after coating and cooling with a high frequency field for a period of 5 minutes and then storage at 2 5 ° C and 45% EH.

The melting point of the emulsion film of each sample was determined 1-, 3- and 7-day storage in a 2% aqueous solution of sodium carbonate determined and the results obtained are given in Table -I below.

Table I.
Melting point ( ⁰ G) in a 2% aqueous sodium carbonate solution

Storage a b C. sample e f F. time (days) 40
58 45
70
> 90 80
> 90 d 73
> 90.
> 90 73
> 90
> 90 I * - - ■
37
40
55 1
3
7th -, 68
> 90
> 90

From the results given in Table I above It can be seen that the irradiated with a high-frequency electric field immediately after coating and cooling Sample (g) was hardened to a lesser extent than Sample (a), so that a poor result was obtained. Samples However, (b) through (f) were well cured and showed good results,

Example 2

To a gelatin silver chlorobromide emulsion with silver chlorobromide particles, which contained 40 mol% silver chloride (1 kg emulsion contained 50 g gelatin and 0.38 mol silver halide) were 20 mg of 2-methoxy-4,6-dichloro-s-triazine per g of dried Gelatin was added, a photographic support was coated with this mixture, so that the dry layer thickness of the coating 5 ρ and then those described in Example 1 were made

Process steps (a) to (g) carried out, the following specified samples (a) to (f) were obtained. The melting point of the emulsion film of each sample was measured in a 2% strength aqueous sodium carbonate solution and the results obtained are given in Table II below.

Table II
Melting point ( ⁰ C) in a 2% aqueous sodium carbonate solution

Storage a _ 36
43
60 b sample C. d e f time (days) 40
48
60 44
50.
63 55
65
65 60
65
68 60
65
68 1
.3
7th

It can be seen from the results in the above table that the hardening of the emulsion film of the samples by irradiation can be noticeably favored with a high-frequency electric field.

Example 3

40 mg of 2,4-dimethoxy-6-chloro-s-triazine per gram of dried gelatin were added to a 5% aqueous gelatin solution and the same procedure as in Example 2 was carried out. samples (a) to (f) shown below were obtained. The melting point of each sample was determined after determined using the same procedure as in Example 1 and the results obtained are given in Table III below.

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gabelle III melting point ( ⁰ G) in a 2% aqueous sodium carbonate solution

Storage a b sample d e f time (days) 36 38 C. 50 • 55 55 1 36 38 42 50 55 55 3 36 38 45 50 55 55 7th 45

It can be seen from the results in the table above that the hardening of the samples can be markedly improved by irradiation with a high-frequency electrical pain.

Example 4

- »

Instead of the 2,4-dimethoxy-6-chloro-striazine used in Example 3 were 30 mg of 2,4-dichloro-6-hydroxyethylamino-s-triazine and the same procedure as in Example 3 was carried out. The melting point of the gelatin film {each sample was determined in a 2% strength aqueous sodium carbonate solution, the results given in Table TV below being obtained became. - -

Table IV Melting point ( ⁰ C) in a 2% aqueous sodium carbonate solution

Storage a b sample d e f time (days ^ 36 38 C. 50 55 55 1 36 38 40 50 55 55 3 36 38 42 50 55 55 7th 42

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From the results of the table above, it can be seen that the hardening of the samples by irradiation with a high frequency electric field can be favored.

Example 5

Instead of the 2,4-dijiethoxy-6-chloro-triazine used in Example 3 were 10 mg of hexahydro-1,3 »5-triacryl-s-triazine and 2 mg of the sodium salt of 2-0xy-4,6-dichloro-s-triazine per gram of dried gelatin and the same procedure as in Example 3 was carried out. The melting point of the gelatin film of each sample was found to be 2% determined aqueous sodium carbonate solution and the results obtained are given in Table V below.

Table Y

Melting point ( ⁰ C) in a 2 # aqueous sodium carbonate solution storage sample

time (days) a b C. d e t 1 36 40 · 45 55 67 45 48 50 60 60 67 7th 60 60 60 60 60 67

From the results of the table above, it can be seen that the hardening of the samples by irradiation with a high frequency electric field was promoted significantly.

Example 6 -

Instead of the 2-oxy-4,6-dichloro-striazine used in Example 1 were 4 mg of 3-Ch} .or-2-phenoxymalaldehyde acid per gram Gelatin was added and the same procedure as in Example 1 was carried out to give the one shown below

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Samples (a) "to (f). The melting point of the emulsion film each Sample was determined in a 2% aqueous sodium carbonate solution and the results obtained are as follows Table VI given.

Table TI

Melting point ( ⁰ C) in a 2% aqueous sodium carbonate solution

Storage a b sample d c e f time (days) 38 42
60 C. 60
85 O IA
VD CO 60
85 Λ
3 " 48
64

7 80 80 85 85 85 85

As can be seen from the results in the table above, was the curing of those irradiated with a high frequency alternating current Sample significantly improved.

Example 7

Instead of the sodium salt of 2-0xy-4,6-difluoro-s-triazine used in Example 1 5 mg of 2,3-dihydroxy-1,4-dioxacn per gram of dried gelatin and the same procedure as in Example 6 was carried out. The melting point of the emulsion film - each sample was in a 2% strength aqueous sodium carbonate solution determined and the resulting Results are given in Table VII below.

Table VII

Melting point ( ⁰ C) in a 2% aqueous sodium carbonate solution storage sample

Time (days) a b C. d e f 1 40 43 50 60 60 6P 3 63 65 70 85 85 85 7th 85 85 85 85 85 85

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As can be seen from the results in the table above, was the hardening of the samples by irradiation with a high frequency electric field significantly promoted.

Example 8

To a 5% aqueous gelatin solution per gram were dried Gelatin 4 mg of mucochloric acid added. A cellulose triacetate film was coated with this solution so that the coating film had a dry thickness of 5 U and

ο,

P?

at

at a moist bulb temperature of 24 C. and at a dry flask temperature of 35 ° C sufficiently dried and then the process steps (a) to (e) given below were carried out, the ones given below in each case Samples (a) to (e) were obtained:

(a) Storage at 25 ° C and 45 % EH for a period of 2 days;

(b) irradiating the sample (a) with a high frequency electrical Field for 30 seconds;

(c) irradiating the sample (a) with a high frequency electrical Field for one minute;

(d) irradiating the sample (a) with a high frequency electrical Field for 3 minutes;

(e) Irradiating the sample (a) with a high-frequency electric field for 10 minutes.

The melting point of the gelatin film of each sample was immediately determined in a 2% aqueous sodium carbonate solution, and the results obtained are shown in Table VIII below.

a b C. Tabel VIII e sample 50 55 60 d 72 M. V \ JJ 69

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The results in the table above show that that the hardening of the gelatin was noticeably promoted even if after the completion of the drying of the gelatin film a high-frequency electric field was applied *

Example 9

3 mg of the sodium salt were added to a 5% strength aqueous gelatin solution of 2-0xy-4,6-dichloro-s-triazine as hardener per gram added dried gelatin, a polyethylene terephthalate film was coated with it to form an 8µ thick Layer (dry layer thickness) and then the process steps indicated below were carried out under Formation of samples (a) to <d):

(a) Immediately after coating and. Cooling irradiation with a high frequency electric field for "50 seconds and subsequent storage at 25 ° 0 and 45% KH;

(b) after completion of drying at constant temperature at a dry flask temperature of 35 ° C and a moist flask temperature of 24- ⁰ C irradiation with a high-frequency electric field for one second and then storage at 25 ° C and 45% EHj.

(c) after completion of drying at constant temperature at

• on the one dry bulb temperature of 35 0 and a wet bulb temperature of 24 ° C irradiation with a high-frequency electric field for 5 seconds and then stored at 25 ⁰ O and 45% EH;

(d) after completion of drying at constant temperature with a dry bulb temperature of 3 5 ° C and a wet bulb temperature of 24 ⁰ C storage at 25 ° C and 45% EH.

The melting point of the gelatin film of each sample after 3 * days Storage was in a 2% aqueous sodium carbonate solution

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and the results obtained are as follows Table ΣΚ given.

Table IX
Melting point ( ⁰ C) in a 2% aqueous sodium carbonate solution

Sample melting point C ⁰ C) a 43

b 63

c 70

d 58

It can be seen from the results in the table above that, when irradiated with a high-frequency electric field immediately after coating, the effect is worse the hardening of the gelatin layer was achieved, but that the hardening of the gelatin was accelerated when the irradiation after completion of the drying at constant temperature, even for a very short period of time, was carried out.

The invention has been described above on the basis of specific embodiments explained in more detail, however, it is clear that they care is not limited and that these can be changed and modified in many ways without thereby affecting the framework the present invention is abandoned

Patent claims:

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Claims (8)

Pa t'e-η tan's sayings Process for the rapid hardening of gelatin, characterized in that that a carrier is coated with an aqueous gelatin solution which, as a hardener, halogenated at least one Diazine compound, a halogenated triazine compound, a Compound with an active vinyl radical, a mucohalo acid or a derivative thereof and / or a substituted or unsubstituted one 2,3-Dihydroxy ~ 1,4 ~ dioxane, and him with dried at a constant speed for a certain time and irradiated with microwaves of a high frequency. 2. The method according to claim 1, characterized in that. the hardener is 4-chloro-2,6-bis (methylsulfonyl) -1,3-diazine, 4-chloro-2-ethylsulfonyl-6-methyl-1,3-diazih, 4,6-bis (methylsulfonyl) -1,3-diazine, 2,4 ~ dibromo-6-methylsulfonyl-1,3-diazine, 2,4,5-tri- * bromo-6-methylsulfonyl-1,3-diazine, 4,5,6-tris (methylsulfonyl) -1,3-diazine, 4-, 5-dichloro-6-methyl-2-phenylsulfonyl-1,3-diazine, 2,3-dichloroquinoxaline-6-carboxylic acid chloride, 2,3-bichloroquinoxaline-S-chloro ^ -sulfonic acid chloride, ISi, N-bis (hydroxyethyl) aminodichlorotriazine, the sodium salt of 2,4-dichloro-6-oxy-s-triazine or 2,4-bis- (1-aziridinyl) -6-chloro-1,3 »5-tjciazin was used. 3. The method according to claim 1, characterized in that the hardener acrylamide, vinyl sulfone, diacryloylamine, dipotassium 1,4-di -. (A-bromoacryloylamino) benzene-2,5-disulfonate, Sodium 2,6-di (bromoacryloylamino) naphthalene-4,6-disulfonate or N-p- (ß-chloroethylamino) sulfobenzene acrylamide is used. · 4. The method according to claim 1, characterized in that one as hardener mucochloric acid, mucobromic acid, 3-bromo-2-phenoxymalaldehyde acid, 3-chloro-2-phenoxymalealdehyde acid, 2- (p-carboxyphenoxy) -3-chloromalealdehyde acid, 2- (p-methoxyphenoxy) -3- 309809/10 81 22A0982 chloromaldehyde acid, 2- (p-tert-pentylphenoxj ^ -chloromaldehyde acid, 2- (p-octylphenoxy) -3-chloromalaldehyde acid, 2- (m-pentadecyl) -3-chloromaldehyde acid or 3-chloro-2-phenylthiomaldehydic acid is used. 5. The method according to claim 1, characterized in that the hardener is 2,3-diforrayl-2,3-dihydroxy-1,4-dioxane or 2,3-diformyl-2,3-dihydroxy-6-methyl-1, 4 ~ dioxane used. 6. The method according to claim 1, characterized in that the hardener in an amount within the range of 1 to 100 mg per gram of gelatin based on dry weight is used. 7. The method according to claim 1, characterized in that one uses microwaves with a frequency for irradiation is within the range of 13 »56 to 18000 MHz. 8. The method according to claim 1, characterized in that for irradiating microwaves with a frequency of 9 ^ 5 MHz or 2450 MHz used. 2 0 9 3 0 9/1081