JPH0850342A - Photographic coating solution - Google Patents

Abstract

PURPOSE:To obtain a photographic coating soln. having a high rate of hardening reaction, causing no coating trouble and free from the malodor of a developing soln. CONSTITUTION:This photographic coating soln. contains at least one kind of compd. represented by the formula, wherein R1 is H, alkyl which may have a substituent or alkoxy, R2 is alkyl which may have a substituent, acyl or acylamino, X is an anion which may form an inner salt and (y) is 1 or 2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic coating liquid, and more specifically, a novel hardener improves the physical properties of a film after coating and does not generate odor due to the accumulation of by-products in the development processing liquid. The present invention relates to a coating liquid.

[0002]

BACKGROUND ART Gelatin is generally used as a binder for photographic coating liquids, and various compounds are used for the purpose of hardening gelatin by the purpose of adjusting the swelling degree of those gelatin layers and increasing the mechanical strength. It has been known. For example, formaldehyde, aldehyde compounds such as glutaraldehyde, compounds having a reactive halogen described in U.S. Pat.No. 3,288,775, U.S. Pat.No. 3,642,486, reactive ethylenically unsaturated compounds described in Japanese Patent Publication No. Sho 49-13563. Having compounds, aziridine compounds described in U.S. Pat.No. 3,017,280, epoxy compounds described in U.S. Pat.No. 3,091,537, halogen carboxyl aldehydes such as mucochloric acid, dihydroxydioxane, dioxane such as dichlorodioxane, or inorganic hardeners. Chromium alum, zirconium sulfate and the like are known as film agents.

However, when these known gelatin hardeners are used in photographic light-sensitive materials, they do not have a sufficient hardening effect, and the hardening effect on gelatin is slow, which is called post-hardening. Changes over time, adversely affecting the performance of photographic materials (increased fog, decreased sensitivity, etc.)
Have some disadvantages, such as those having the above-mentioned properties, or the co-existence of other photographic additives losing the hardening effect, or the effects of other photographic additives (for example, color formers for color light-sensitive materials) being reduced. It was

The dura mater reaction to gelatin is relatively fast,
As a hardener with little post-hardening, compounds having a dihydroquinoline skeleton described in JP-A-50-38540, JP-A-58-113
Phosphorus-halogen bond described in 929, described in JP-A-52-93470
Compounds with N-sulfonyloxyimide groups, Japanese Patent Publication No. 53-2
Compounds having two or more N-acyloxyimino groups in molecule 2089, JP-B-56-12853 and JP-B-58-32699
N-carbamoylpyridinium salts described in JP-A-56-110
There are known 2-sulfonyloxypyridinium salts described in JP-A No. 762, carbamoylpyridinium compounds having an alkyl ester substituent on the pyridine ring described in JP-A-6-12408, and the like.

In particular, the hardener described in JP-B-58-32699 has a high degree of curing, high water solubility and does not require a special organic solvent for coating a gelatin film, but the viscosity of the coating solution increases during production. It has the drawback of making coating difficult and causing coating failure. Further, the compound described in JP-B-56-12853 has a drawback that amine, which is a by-product after the hardening reaction, elutes and accumulates during the development process to generate an odor, which harms the working environment.

Accordingly, there has been a demand for a gelatin hardener which has a small amount of after-hardening, has no coating failure, and has no amine odor as a by-product accumulated in the developer.

[0007]

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is to provide a photographic coating solution which has a fast hardening reaction, does not cause coating failures, and has no amine odor as a by-product due to the accumulation of developing solution. Is provided.

[0008]

As a result of intensive studies, the present inventors have found that the above object can be achieved by using a compound represented by the following general formula [1] as a hardening agent for gelatin.

A photographic coating liquid containing at least one compound represented by the following general formula [1].

[0010]

Embedded image

R ₁ represents a hydrogen atom or an alkyl group or alkoxy group which may have a substituent, R ₂ represents an alkyl group, an acyl group or an acylamino group which may have a substituent, and X represents an anion. Represents an ion, y is 1 or 2, and when y is 1, an intramolecular salt is formed.

In the general formula [1], R ₂ is an alkylenesulfonic acid or an acylamino group, and the photographic coating liquid is described.

In the general formula [1], R ₂ is-(-
CH ₂ −) m−SO ₃ ⁻ , −NR ₃ COR ₄ , − (− CH ₂ −) p−CONR ₇ R ₈ ,
− (− CH ₂ −) q−NR ₉ R ₁₀ , − (CH ₂ −) s−CH− (LR ₁₂ ) −R ₁₁
The stands, R ₃ represents an alkyl group which may have a hydrogen atom or a substituent, R ₄ represents an alkyl group which may have a substituent, an alkoxy _{group, -O - (- CH 2 -} ) n- ^{_{SO 3 -, -NR 5 R 6}} ,
_{- (- CH 2 -) n} -SO 3 - represents, R _5, R ₆ is a hydrogen atom or a substituent alkyl group which may have a _{- (- CH 2 -) n} -SO 3 - represents, R ₇ represents a hydrogen atom or an alkyl group or aryl group which may have a substituent, R ₈ represents a hydrogen atom or an alkyl group which may have a substituent, or R ₇ and a 5- or 6-membered aliphatic ring. R ₉ represents a hydrogen atom or an alkyl group which may have a substituent or -COR ₄ , and R ₁₀ represents a hydrogen atom or an alkyl group which may have a substituent or-(- CH ₂
−) R—SO ₃ ^— , L represents —O—, —NR ₁₃ —, R ₁₁
Represents a hydrogen atom or an optionally substituted alkyl group, R ₁₂ represents a hydrogen atom or an optionally substituted alkyl _{group, -COR 14, -CONHR 15, R} 13, R 14, R ₁₅ represents a hydrogen atom or an alkyl group which may have a substituent, m
Is 0, 2 to 4, n is 1 to 3, p is 0 to 2, q and r are 1
~ 3, s is a coating solution for photography as described in 2-3.

In the general formula [1], R ₁ is a hydrogen atom or an alkyl group or an alkoxy group which may have a substituent, and R ₂ is — (— CH ₂ —) m—SO ₃ ^— or —NR. ₃ COR ₄ is a coating liquid for photography as described above.

The compounds used in the present invention will be exemplified below, but the present invention is not limited thereto.

[0016]

[Chemical 3]

[0017]

[Chemical 4]

[0018]

Embedded image

[0019]

[Chemical 6]

These compounds can be easily synthesized by the methods described in the literature. For example, “Chem.Ber. Volume 40 1831
Page (1907) "and J. Phys. Chem. Vol. 68, page 3149".

The synthetic examples of these compounds are shown below.

Synthesis of Exemplified Compound (4) 10 g of 4-aminopyridine in acetonitrile (150 ml) was heated to 60 ° C., 15 g of chloroacetyl chloride in acetonitrile (40 ml) was added dropwise, and then heated to 90 ° C. under reflux.
It was stirred for 12 hours. After cooling to room temperature, the precipitated crystals were collected by filtration and dried to obtain 41.5 g of 4-chloroacetamidopyridine.

4-chloroacetamidopyridine 2 obtained in an aqueous solution of 26 g of sodium sulfite (dissolved in 900 ml by heating)
1.5 g of an aqueous solution (200 ml) was added dropwise, and the mixture was stirred at 75 ° C for 12 hours. Then, 10 ml of concentrated hydrochloric acid was added, and the mixture was stirred at room temperature for 1 hour. The precipitated crystals were collected by filtration, washed with water and dried to obtain 20 g of 4-sulfoacetamidopyridine.

Obtained 4-sulfoacetamidopyridine 20
g and tripropylamine (15 g) were dissolved in an acetonitrile solution (heat dissolved in 50 ml), 20 g of pyrrolidinocarbonyl chloride was added dropwise, and the mixture was stirred at 75 ° C. for 12 hours. The precipitated crystals were collected by filtration and dried to obtain a hardener (4) (14 g). The chemical structure was confirmed by various spectra and elemental analysis.

Synthesis of Exemplified Compound (5) 4-Pyridineethanesulfonic acid (20 g) and tripropylamine (17 g) were dissolved in acetonitrile (60 ml), pyrrolidinocarbonyl chloride (16 g) was added dropwise, and the mixture was stirred at room temperature for 12 hours. The precipitated crystals are collected by filtration and dried to give a hardening agent (5) 25.5 g.
I got The chemical structure was confirmed by various spectra and elemental analysis.

These compounds are dissolved in water or a hydrophilic solvent such as methanol or ethanol and then added to the photographic coating liquid according to the present invention.

The gelatin layer formed by the coating solution according to the present invention includes, for example, a photosensitive or non-photosensitive silver halide emulsion layer, an intermediate layer, a filter layer, an antistatic layer, a development control layer, an undercoat layer and a halation. It is a photographic constituent layer containing gelatin such as an prevention layer and a backing layer. The amount of the compound of general [I] of the present invention to be used in these layers is not uniform depending on the compound or the kind of the coating liquid, but 0.01 to 2.0 mmol per 1 g of the dry weight of gelatin which is usually used. Is preferable, and a range of 0.03 to 1.0 mmol is more preferable.

The compound of the above-mentioned general formula [1] of the present invention may be used in combination with other known hardeners, and specific examples of known hardeners that can be used in combination include formalin, glyoxal and succinaldehyde. Aldehyde type compounds, such as
Examples thereof include acid-releasing triazine compounds such as sodium 2,4-dichloro-6-hydroxytriazine, and vinyl sulfone type compounds described in JP-B-47-6151.

The silver halide grains used in the present invention are
Normal crystal (cubic, octahedral, and tetradecahedral) grains are also preferable, and tabular grains are more preferable. The average grain size of silver halide grains is preferably 0.2 to 2.5 μm, particularly preferably 0.4 to 2.5 μm.
It is 2.0 μm.

The tabular silver halide grains according to the present invention are
The average value of particle diameter / thickness (called aspect ratio) (called average aspect ratio) is 3 or more, preferably 3 to
30 is more preferable, 3 to 20 is more preferable and 3 to 20 is particularly preferable.
Is 10.

The average thickness of the tabular silver halide emulsion according to the present invention is preferably 0.4 μm or less, more preferably 0.3 μm.
Below, it is particularly preferably 0.05 to 0.25 μm.

In the present invention, the diameter of the silver halide grain is defined as the equivalent spherical diameter of the grain from the observation of an electron micrograph of the silver halide grain.

In the present invention, the thickness of the silver halide grain is defined as the minimum distance between the two parallel planes constituting the tabular silver halide grain. The thickness of tabular silver halide grains can be determined from electron micrographs of silver halide grains shaded or electron micrographs of sample slices obtained by coating a support with a silver halide emulsion and drying.

To obtain the average aspect ratio, the minimum
Measure 100 samples.

In the silver halide emulsion according to the present invention,
The proportion of tabular silver halide grains in all silver halide grains is preferably 50% or more, more preferably 60% or more,
It is particularly preferably 70% or more.

The tabular silver halide emulsion according to the present invention is preferably one which is monodisperse, and contains 50% by weight or more of silver halide grains contained in a grain size range of ± 20% around the average grain size. Those of are particularly preferably used. It is also preferable to use monodisperse particles as a mixture, and in this case, the particle size distribution of the particles in the photosensitive material has two or more maximum values.

The tabular silver halide emulsion according to the present invention comprises
The halogen composition such as silver chloride, silver bromide, silver chloroiodide, silver chlorobromide, silver iodobromide and silver iodobromide is optional, but silver iodochlorobromide is preferred from the viewpoint of high sensitivity, and the average iodine The silver halide content is 0 to 4.
It is 0 mol%, particularly preferably 0.2 to 3.0 mol%, and the average silver chloride content is 0 to 5 mol%. Further, in the tabular silver halide emulsion according to the present invention, the halogen composition may be uniform within the grain, or silver iodide may be localized, but the one localized in the central portion is preferable. It is preferably used.

The method for producing a tabular silver halide emulsion is described in JP-A Nos. 58-113926, 58-113927, 58-113934 and 6-113.
It is also possible to refer to 2-1855, European Patents 219,849, 219,850 and the like.

Further, JP-A-61-6643 can be referred to as a method for producing a monodisperse tabular silver halide emulsion.

As a method for producing a tabular silver iodobromide emulsion having a high aspect ratio, an aqueous solution of silver nitrate or an aqueous solution of silver nitrate and an aqueous solution of halide are simultaneously added to a gelatin aqueous solution having pBr of 2 or less to form seed crystals. It can be obtained by generating and then growing by the double jet method.

The size of tabular silver halide grains can be controlled by the temperature at the time of grain formation and the rate of addition of an aqueous silver salt and halide solution.

The average silver iodide content of the tabular silver halide emulsion can be controlled by changing the composition of the aqueous halide solution to be added, that is, the ratio of bromide to iodide.

Further, during the production of tabular silver halide grains,
If necessary, a silver halide solvent such as ammonia, thioether or thiourea can be used.

The emulsion may be subjected to a water washing method such as a noodle water washing method or a flocculation sedimentation method in order to remove soluble salts. A preferred washing method is disclosed in
The method using an aromatic hydrocarbon-based aldehyde resin containing a sulfo group described in JP-A No. 35-16086, or the method using an aggregating polymer agent exemplified G-3, G-8 described in JP-A-2-7037 is particularly preferable. The salt method can be mentioned.

The emulsion used in the photographic coating liquid of the present invention can be produced by a known method. For example, Research Disclosure (RD) No.17643 (December 1978), 22-
Page 23 1. Emulsion Preparation and typ.
es) and the same (RD) No. 18716 (November, 1979), by the method described on page 648.

The emulsion of the photographic coating solution according to the present invention is described in, for example, "The theory of the photographic pr" by TH James.
ocess ”, 4th edition, published by Macmillan (1977), pages 38-104, GF Daufin,“ Photoemulsion Chemistry, ”“ Photogr.
aphic Emulsion Chemistry ”, published by Focal press (1966
,) "Physics and Chemistry of Photography" by P. Glafkides "Chimieet
physique photographique ”published by Paul Montel (1967
), VL Zelikman et al., "Making and Coating Photographic Emulsions""M
aking and Coating photographic Emulsion ”Focal pre
It is prepared by the method described in ss company (1964).

That is, the solution conditions such as the neutral method, the acidic method, the ammonia method, etc., the forward mixing method, the reverse mixing method, the double jet method, the controlled double jet method and the like, the conversion method, the core / shell method. It can be produced using the particle preparation conditions such as and the like and a combination method thereof. One of the preferred embodiments of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains.

In the emulsion according to the present invention, various photographic additives can be used in the steps before and after physical ripening or chemical ripening. Known additives include, for example, Research
Disclosure (RD) 17643, (RD) 18716
(November 1979) and (RD) 308119 (December 1989). These three (R
The types and locations of the compounds described in D) are listed below.

Additive RD-17643 RD-18716 RD-308119 Page classification Page classification Page classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IVA Desensitizing dye 23 IV 998 IVB Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Surfactant 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 right 1006-7 XIII plasticizer 27 XII 650 right 1006 XII slip agent 27 XII matting agent 28 XVI 650 right 1008-9 XVI binder 26 XXII 1003-4 IX support 28 XVII 1009 XVII according to the present invention Examples of the support that can be used in the light-sensitive material include the above-mentioned (RD) -17643, page 28 and (RD).
-308119, page 1009.

A suitable support is a plastic film or the like, and the surface of these supports may be provided with an undercoat layer for improving the adhesion of the coating layer, corona discharge, ultraviolet ray irradiation or the like.

Examples of photographic coating solutions to which the present invention can be applied include direct X-ray films, indirect films, inversion films for duplication, films for CT imagers, films for laser imagers, gravure films for printing plate making, Examples thereof include a line drawing film, a film for halftone dot shooting, a film for returning film, a film for monochrome shooting, and a film for color shooting.

The light-sensitive material formed from the photographic coating liquid of the present invention can be developed by a known method. For example, any of various methods and various processing solutions as described in Research Disclosure (RD) 17643 can be used.

[0053]

EXAMPLES The present invention will be described below with reference to examples, but it goes without saying that the present invention is not limited to the examples.

Example 1 Monodispersed cubic crystal grains of silver iodobromide containing 2.0 mol% of silver iodide having an average grain size of 0.20 μm were controlled by a double jet method while controlling 60 ° C., pAg = 8.0 and pH = 2.0. Obtained.

A part of this emulsion was used as a seed and grown as follows. That is, in a solution containing seed particles and gelatin
A solution containing an ammoniacal silver nitrate solution and potassium iodide was added by a double jet method at 40 ° C., pAg = 8.0 and pH = 9.5 to form a first coating layer containing 25 mol% of silver iodide. The addition rate was gradually increased as the particles grew.

The resulting emulsion was an octahedral monodisperse emulsion having an average grain size of 0.45 μm. Using the emulsion grains as cores, an aqueous ammoniacal silver nitrate solution and an aqueous potassium bromide solution were added at a pAg of 11.0 and a pH of 9.0 by the double jet method to form a second coating layer. It was an octahedral monodisperse emulsion having an average grain size of 0.80 μm.

To the above emulsion, ammonium thiocyanate (1.8 × 10 ^-3 mol per mol of silver halide) and chloroauric acid and sodium thiosulfate were added to perform chemical ripening, and then an emulsion coating solution having the following composition was prepared. did.

(Composition of emulsion coating liquid) Per liter of coating liquid Lime-treated ossein gelatin 51 g 5-methyl-1,3,4,7a-tetrazaindene-7-ol 0.8 g The above silver halide emulsion 0.6 mol 1- Phenyl-5-mercaptotetrazole 0.015 g The following coating solution for protective layer was prepared.

(Composition of coating liquid for protective layer) Per liter of coating liquid Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g

[0060]

[Chemical 7]

Hardener shown in Table 1 Amount shown in Table 1 Polymethylmethacrylate (matting agent having an area average particle size of 5.0 μm) 1.1 g Emulsion layer has a gelatin amount of 2.1 g / m ^{2 on} one side, and a protective layer has gelatin. Both sides were simultaneously coated on the polyethylene terephthalate support in a multi-layered manner at a rate of 140 m / min so that the amount was 0.98 g / m ² per side and dried.

The obtained sample film was heated at 23 ° C. and a relative humidity of 50.
%, And after 4 hours, 1 day, 3 days, and 7 days after application, the melting time was measured by the following method. The sample was dipped in a 1.5% sodium hydroxide solution kept at 60 ° C., and the time until the gelatin began to dissolve was taken as the melting time. The measurement results are shown in Table 1.

Further, an XD-SR developer (Konica Corporation)
100 ml was kept at 35 ° C, and the sample film stored under the above conditions was cut into four pieces and cut into three pieces (0.2325 m ² ).
The odor of the developing solution after the immersion treatment for 15 seconds was evaluated according to the following evaluation criteria, and the results are shown in Table 1.

A: Equivalent to a non-processed film developing solution (blank) B: Slight odor from blank (practical) C: Smell from blank (practical)

[0065]

[Table 1]

[0066]

Embedded image

The hardener (D) was unable to be applied because the viscosity of the protective layer coating solution increased during application, and gelled 10 minutes after addition of the hardener.

As is clear from the results of Table 1, samples using the hardeners (2), (5), (8) and (10) of the present invention and the comparative hardeners (D) and (E). Has a rapid hardening effect and the melting time stabilizes one day after application, and does not increase thereafter.
It can be seen that the samples using the comparative hardening agents (A), (B) and (C) have a slow hardening effect and the melting time is increased (post-hardening) even after 3 days. Further, with respect to the hardener (D), the film was hardened too fast, and the viscosity of the coating solution increased in a short time, making it difficult to apply. The developer treated with the film using the hardener (E) had a strong amine odor.

[0069]

INDUSTRIAL APPLICABILITY According to the present invention, a photographic coating solution containing at least one compound represented by the general formula [1] is excellent in coating property and has no change in performance upon storage over time. A coating solution for photographic use was obtained in which no odor was generated by a compound that was a by-product or accumulated therein.

Claims (4)

[Claims] 1. A photographic coating solution containing at least one compound represented by the following general formula [1]. Embedded image R ₁ represents a hydrogen atom or an optionally substituted alkyl group or alkoxy group, R ₂ represents an optionally substituted alkyl group, an acyl group or an acylamino group, and X represents an anion. , Y is 1 or 2, and y is 1
When, an inner salt is formed. 2. The photographic coating liquid according to claim 1, wherein R ₂ in the general formula [1] is an alkylene sulfonic acid or an acylamino group. 3. In the general formula [1], R ₂ is-(-CH
₂ −) m−SO ₃ ⁻ , −NR ₃ COR ₄ , − (− CH ₂ −) p−CONR ₇ R ₈ , −
_{(-CH 2 -) q-NR} 9 R 10, - the s-CH- (LR ₁₂₎ represents a -R _11, R ₃ is an alkyl group which may have a hydrogen atom or a substituent - (CH ₂₎ R ₄ is an alkyl group which may have a substituent,
_{Alkoxy, -O - (- CH 2 -} ) n-SO 3 -, -NR 5 R 6, -
_{(-CH 2 -) n-SO} 3 - represents, R _5, R ₆ is a hydrogen atom or an alkyl group which may have a _{substituent, - (- CH 2 -)} n-SO 3 - represents, R ₇ represents a hydrogen atom or an alkyl group or an aryl group which may have a substituent, R ₈ represents a hydrogen atom or an alkyl group which may have a substituent, or R ₇ and a 5- or 6-membered aliphatic ring. Represents a group to be formed, R ₉ represents a hydrogen atom or an alkyl group which may have a substituent or -COR ₄ , and R ₁₀ represents a hydrogen atom or an alkyl group which may have a substituent or-(-CH
₂ −) r—SO ₃ ^— , L represents —O— or —NR ₁₃ —,
R ₁₁ represents an alkyl group which may have a hydrogen atom or a substituent, R ₁₂ represents a hydrogen atom or an optionally substituted alkyl _{group, -COR 14, -CONHR 15, R} 13, R ₁₄ , R ₁₅ represents a hydrogen atom or an alkyl group which may have a substituent,
m is 0 or 2-4, n is 1-3, p is 0-2, q and r
Is 1 to 3 and s is 2 to 3. The photographic coating liquid according to claim 1. 4. In the general formula [1], R ₁ is a hydrogen atom or an alkyl group or an alkoxy group which may have a substituent, and R ₂ is — (— CH ₂ —) m—SO ₃ ^— or The coating solution for photography according to claim 1, which is -NR ₃ COR ₄ .