JPS6256952A - Production of photo sensitive material - Google Patents

Abstract

PURPOSE:To improve the wettability of the titled material against the hotographic processing solution, and to prevent the generating of a foam in a rapidly developing process and to stabilize the photographic processing properties by providing a photographic constituent layer which incorporates a low molecular weight gelatin and a polymer latex in a hydrophilic colloid on the titled material. CONSTITUTION:The photographic constituent layer incorporating the low molecular weight gelatin and the polymer latex in the hydrophillic colloid is coated on the titled material. Thus, the low molecular weight gelatin contd. in the photographic constituent layer has an effect of an excellent coating auxiliary. The dispersion of a coupler, an UV absorbing agent and an another hydrophobic photographic additive to the hydrophilic colloid layer easily makes. And then, the prescribed gelatin may be added to either a photosensitive layer or a non-photosensitive layer. The uniform hydrophillic colloidal coating film is formed, and the unevenness of the coating and the repelling of the coating film do not generate by incorporating the low molecular weight gelatin to the titled material in the low speed coating as well as the high speed coating of the emulsion. The obtd. photosensitive material improves the wetting of the titled material against the photographic processing solution, and lessened the generation of the foam and enables to the evenness and stable developing process. Especially, the titled material is useful to the processing of the printing sensitive material.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field 1] The present invention relates to a method for producing a photographic light-sensitive material, and more specifically, a photographic light-sensitive material having improved photographic properties and processability and good film properties. Relating to a manufacturing method.

[Background of the Invention] In general, hydrophilic colloid films used to produce photographic materials are required to have specified strength not only in terms of photographic properties but also in terms of physical properties of the film. Attempts have been made to improve the physical properties of the hydrophilic colloid layer, such as scratch strength, dimensional stability, and flexibility, by incorporating various polymer latexes into the hydrophilic colloid. For example, U.S. Patent No. 2.852.386, U.S. Pat.
The technique is disclosed in Japanese Patent Application Publication No. 57-9051, Japanese Patent Application Laid-Open No. 57-200031, and the like.

Surfactants are used in large quantities as dispersion stabilizers during the production of such polymer latexes, but these surfactants affect photographic properties such as photographic sensitivity, fog, and gradation, depending on the type and direction of addition. , it may have a negative effect on the speed of development, such as the speed of development (e.g., good wetness on the film surface, no adhesion of bubbles on the film surface, etc.), and improvement is desired. be done.

[Object of the Invention] - Therefore, the first object of the present invention is to provide a silver halide photographic material in which a photographic constituent layer consisting of a hydrophilic colloid such as a binder is uniformly coated on a support. .

A second object of the present invention is to provide a method for producing a silver halide photographic material containing a coating aid that does not substantially adversely affect photographic properties such as photographic sensitivity, fog, gradation, and development speed. There is a particular thing.

The third object of the present invention is that the manufactured silver halide photographic light-sensitive material has good wettability with a photographic processing solution, does not generate bubbles, and is free from unevenness even when developing processing is carried out automatically at high speed. It is an object of the present invention to provide a method for producing a silver halide photographic material that can obtain stable photographic processing characteristics.

A fourth object of the present invention is to provide a method for producing a silver halide photographic material with improved film properties such as scratch strength, dimensional stability, and flexibility.

[Structure of the Invention] The above objects of the present invention are achieved by a method for producing a photographic light-sensitive material, which is a method for producing a photographic light-sensitive material, which comprises coating a photographic constituent layer containing a hydrophilic colloid.

[Specific structure of the invention] Low molecular m contained in the photographic constituent layer in the present invention
The gelatin is preferably a gelatin with an average molecular weight of less than s, ooo, and acts as an excellent coating aid, especially for use in lipophilic photographs such as couplers, ultraviolet absorbers, optical brighteners, etc. into hydrophilic colloid layers. It has excellent performance in dispersing additives.

The low molecular weight gelatin used in the present invention is obtained by hydrolyzing collagen, which is the main protein that makes up animal bones, skin, and the like. Gelatin hydrolysis methods are well known, and those skilled in the art can easily obtain low-molecular-weight gelatin. Also, such gelatin is N [KKOL
ccp -40” (average molecule 1i1400), “N
IKKOL ccp -100” (average molecular ff1l
OOO) It is commercially available under the trade name [Nikko'r Micalus@].

The average molecular weight of gelatin referred to here is H
It is calculated using a CC-802AGPC device in terms of standard polystyrene.

The low molecular weight gelatin used as a coating aid in the present invention preferably has an average molecular weight of 5,000 or less, more preferably 3,000 or less.

The low molecular weight gelatin used in the present invention is added in a range of 0.01 to 5 g (+) per 1 kg of various photographic coating solutions, but usually 0.05 to 5 g is suitable. Alternatively, it is preferably added as a solution dissolved in methanol or other water-miscible solvent.The gelatin according to the present invention may be added to the coating solution of any photographic constituent layer constituting the photographic light-sensitive material. It does not matter whether the layer is a photosensitive layer or a non-photosensitive layer. Examples of the photosensitive layer include a silver halide emulsion layer, and examples of the non-photosensitive layer include an undercoat layer, an intermediate layer, a surface protective layer, etc. It will be done.

According to the method for producing a light-sensitive material of the present invention, the present invention I; by adding such low molecular weight gelatin, hydrophilic colloids are extremely uniformly coated not only in low-speed coating of emulsions but also in high-speed coating (50+e/min or more). A coating film is formed. In other words, uneven coating of the emulsion and repellency of the coating film do not occur.

Regarding photographic properties, the present invention is extremely useful especially when applied to photosensitive materials for printing. For example, development progress is extremely important for lithium-type photosensitive materials that require very high contrast to be obtained under predetermined development conditions (time), and surfactants in particular affect the development progress of lithium-type photosensitive materials. Although the low-molecular-weight m-gelatin used in the present invention does not substantially change the development progress of the lithium-type light-sensitive material, although it often affects the development process.

The low molecular weight gelatin according to the present invention is useful when containing lipophilic substances such as couplers, alkylhydroquinones, ultraviolet absorbers, and sensitizing dyes, hydrophobic vinyl polymers, etc. in photographic light-sensitive materials. Useful for dispersing polymer latexes of hydrophobic vinyl polymers.

The lipophilic substance is dissolved in a water-soluble organic solvent with a high boiling point, and the resulting solution is finely and stably dispersed in an aqueous hydrophilic colloid solution in the presence of the low molecular weight gelatin of the present invention, and this is directly applied as a coating solution. It can be used or further added to coating solutions such as photographic emulsions.

In the method for producing a photographic material of the present invention, a polymer latex is present in the hydrophilic colloid in order to improve the physical properties of the film. Such a polymer latex can be easily produced by redispersing a polymer obtained by a known emulsion polymerization method, solution polymerization method, or bulk polymerization method. As the polymerization method, emulsion polymerization method is preferred. In this emulsion polymerization method, the reaction temperature is 20 to 180°C,
More preferably at 40 to 100°C, with water and 1
0 to 50% by weight of a hydrophobic vinyl monomer, 0.05 to 5% by weight of a polymerization initiator based on the monomer, and 0.1 to 2% by weight of a polymerization initiator.
It is carried out using 0% emulsifier.

At this time, the low molecular weight gelatin of the present invention can be present. Furthermore, the polymerization initiator, concentration, reaction temperature, reaction FR range, etc. can be varied widely and arbitrarily depending on the purpose. Although the emulsifier can generally be synthesized without using it, it is preferable to use it in view of the stability of the resulting polymer latex over time, its compatibility with hydrophilic colloids, etc.

When the compound of the present invention is present during polymerization, the low molecular weight gelatin of the present invention can be used as part or all of the stone added to the photographic coating solution.

Examples of emulsifiers used in the polymerization of the polymer latex of the present invention include anionic, cationic, amphoteric, and nonionic surfactants as well as water-soluble polymers. It is preferable to use

Examples of the polymerization initiator used in the emulsion polymerization method for polymer latex of the present invention include persulfate fa salts such as potassium persulfate, ammonium persulfate, and sodium persulfate;
4.4'~Sodium azobis-4-cyanovalerate, 2
,2'-azobis(2-amidinopropane) salt F! Water-soluble azo compounds such as salts and hydrogen peroxide can be used.

The molecular weight of the polymer latex of the present invention is 2,000 to 1
,000. Goo is preferred, Gets is more preferred,
000-50G, Goo. Particle size is 0.01~1μ
− is preferable, and 0.01 to 0.5 μ− is more preferable.

The monomer used to obtain the polymer latex is not particularly limited as long as it is a polymerizable ethylenic monomer, but preferably a hydrophobic monomer. Examples of such hydrophobic vinyl esters include acrylic esters, methacrylic esters, vinyl acetate, styrene, vinyl chloride, vinylidene chloride, butadiene, etc. In particular, acrylic esters, methacrylic esters and the present invention It is compatible with low molecular weight gelatin.

The acrylic esters include methyl acrylate, ethyl acrylate, n-propyl acrylate,
Isopropyl acrylate, n-butyl acrylate,
Isobutyl acrylate, 5ec-butyl acrylate, tert-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl 7-acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chloro butyl acrylate,
Cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimedylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-
cyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 2-droxyethyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypentyl acrylate, 2- methoxyethyl acrylate,
3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 'l-1so-propyl acrylate, 2-butoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2=(2-butoxyethoxy)ethyl acrylate, ω- Methoxypolyethylene glycol acrylate (number of moles added n-9), 1
-Bromo 2-methoxyethyl acrylate, 1゜1-
Examples include dichloro-2-ethoxyethyl acrylate.

Further, examples of the methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 5e
c-Butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, RIOO benzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2-(
3-phenylpropyloxy)ethyl methacrylate,
Dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, talesyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2 -Methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-
(2-methoxyethoxy)ethyl methacrylate, 2-
(2-ethoxyethoxy)ethyl methacrylate, 2-
(2-Butoxyethoxy)ethyl methacrylate, ω-
Examples include methoxypolyethylene glycol methacrylate (additional mole number n=6), allyl methacrylate, and methacrylic acid dimethylaminoethyl methyl chloride salt.

The polymer latex of the present invention is preferably 80% by weight or less, more preferably 5% by weight or less based on the hydrophilic colloid.
50% by weight, and the coating amount is approximately 0.01 per 1f.
(7-5.Og is preferable, more preferably 0.1g-
It is 1.0g.

Hydrophilic colloids used in the method for producing photographic materials of the present invention include, in addition to gelatin, which is the most typical, cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, synthetic polymers such as polyacrylamide, etc. alone or in mixtures. . Water-insoluble polymers such as polyalkyl acrylates or polyalkyl methacrylates may also be dispersed in such hydrophilic colloids.

The photographic material of the present invention includes silver chloride, silver bromide, silver iodide,
Silver halides used in ordinary photographic materials such as silver chlorobromide, silver iodobromide, and silver chloroiodobromide are used.

In addition to silver halide photographic emulsions, there are also direct positive photographic emulsions that have silver halide grains whose surfaces have been fogged with light, reducing substances, noble metal salts, etc., and internal latent image photographs that produce positive images through surface development. Emulsions can also be used.

The silver hegenide emulsion may be chemically sensitized with a sulfur compound, selenium compound, noble metal compound, or the like, or spectrally sensitized with a sensitizing dye in a conventional manner.

The coating liquid used to form the photographic constituent layer according to the present invention includes inorganic hardeners such as chromium alum, chromium acetate, etc., formaldehyde, mucochloric acid, active halogen compounds, active vinyl compounds, ethyleneimide compounds, etc. It may also contain various photographic hardeners such as organic hardeners.

The photographic light-sensitive material of the present invention may contain various emulsion stabilizers such as azaindene compounds and phenylmercaptotetrazole, antifoggants, and the like. In addition, various additives necessary to obtain photographic materials, such as surface-modifying detergents such as silicones, fluorine-containing compounds, and aliphatic esters,
Various color couplers and dyes in color photosensitive materials,
It may contain a plasticizer or the like.

[Example] The present invention will be explained in more detail with reference to Examples below. Note that all percentages are by weight unless otherwise specified.

Example 1 Silver chlorobromide emulsion containing 7% gelatin and 5% silver halide (
Collagen peptide [NIKKOL CCP-4 (Nikko'
y Mika/shiX111) ] (D O,2(l ト0.
05μm polyethyl acrylate latex isog
(solid content 20% by weight) was added. This photographic emulsion was coated on baryta paper by a dip method at a coating speed of 50 m/min, and cooled and set. On top of this, a collagen peptide with an average molecular weight of 40 G [
NIKKOL ccp-4 (Nikko Chemicals @I
I)] and 1 oog of polyethyl acrylate latex having a particle size of 0.05μ (solid content 20% by weight)
) was coated, cooled, and then dried. There were no bubbles or repellents in the emulsion layer and the M retention layer of the produced film, and uniform coating was possible at a coating speed of 50 mol/min. In addition, when these samples were developed with a normal methol-hydroquinone developer, the photographic properties (
No adverse effects were observed on sensitivity, gamma, fog).

Example 2 A high-sensitivity, high-contrast emulsion containing 6% gelatin and 6% silver iodobromide (silver iodide 1.5 mol%) was prepared. This photographic emulsion contains collagen peptide (NIKKOL) with an average molecular weight of 51iooo.
ccp-10) from 0.01Q per 1kll+ emulsion
It was added as a 2% aqueous solution to contain 2.5 g of polyethyl acrylate latex, and 150 g of polyethyl acrylate latex was added.
<1 (solid content 207148%) was added.

This emulsion was coated on a cellulose triacetate support with a subbing layer and dried. As shown in Table 1, the average molecule is 1100
G collagen peptide (NIKKOLccp-10)
It can be seen that the number of repellents decreases significantly as the amount of addition increases.

Below is a margin Table 1 Example 3 An antihalation layer containing a water-soluble magenta dye, gelatin, and an ethyl acrylate polymer prepared in Formulation 1 below on one side of a polyethylene terephthalate support having subbing layers on both sides. Apply it. On the other hand 4.
5wt 6% gelatin and 19.5 mol% silver bromide, 801
3-hydroxymethyl-
5-[2-(3-ethylthiazolinidene)ethylidene] rhodanine, 4-human 0x-1,3,3a, 7-chitrazaindene, mucochloric acid, polyoxyethylene nonylphenyl ether containing 50 eblene oxide groups and N-(γ-diethylaminepropyl)-N'-phenylurea, respectively, were added rapidly in the usual manner, then divided into two equal parts, and the first part was further divided into four equal parts, each of which was given the following formulation (1).
20 G of the ethyl acrylate polymer dispersion prepared according to (4) was added to 1 kQ of the emulsion, and the mixture was thoroughly stirred and mixed. No dispersion is added to the remaining portion.

Each portion of the emulsion was coated on the side of the support opposite the antihalation layer at a ratio of 55±5 mg silver per GOf.

Prescription (1) Distilled water 12j! To the mixture were added 3 ko of ethyl acrylate and 100 g of low-molecular-member gelatin with an average molecular weight of 4 GG as a dispersant, and the mixture was stirred at 500 to aoarp- to emulsify. Next, add 0.15% of potassium persulfate (+) as a polymerization initiator, and heat while stirring and keep at 90 to 100°C. If the reaction continues for 6 hours, the polymerization will be completed. To remove some residual monomer, add 1. By carrying out steam distillation for a period of time, the desired stable aqueous dispersions of ethyl acrylate polymer can be obtained.The particle size of the solid vinyl polymer in these dispersions is approximately 0.
The particles were spherical particles with a diameter of 0.02 to 0.1μ, and most of them were approximately 0.05μ.

Formulation (2) Preparation was made in the same manner as in Formulation (1) except that the anionic surfactant <a> shown below was used in place of the low molecular weight gelatin. This is referred to as Comparative Example 1.

(a) CrzHtr O*CHzCHz05CHt5SOsN
Prescription a (3) Prescription (1) was followed using the following anionic surfactant (b) instead of low molecular weight gelatin.

This is comparative example 2.

Prescription (4) Prescription (1) was followed using sodium dodecylbenzenesulfonate (abbreviated as SO8) instead of low molecular weight gelatin. This is comparative example 3.

Prescription (5) Prescription (1) was followed using low molecular weight ω gelatin 50 (+) and the above anionic surfactant (a) 50.1 instead of low molecular weight gelatin 100Q.

On top of each coated emulsion layer, a 6% gelatin aqueous solution, low molecular gelatin with an average molecular weight of 140 G, the above surfactants (a), (b), SO3, and the low molecular weight gelatin and the above surfactant (a) were added. A coating solution in which 100 mg of each 1:1 mixture was added to a 1 kQ gelatin aqueous solution was applied in the combinations shown in Table 2 so that the dry film thickness was 1 μm to form a protective layer.

Using a tungsten light source for each of these sample films,
1/2 of the area of each sample was exposed to light through a 150-line magenta contact screen, and the remaining 1/2 was exposed to light in a wedge manner, using developers I and II shown in Table 3. , development processing was carried out at a development temperature of 25° C. and a development time of 2 minutes.

After the development process, the photographic sensitivity was measured and the halftone dot quality was observed using an optical microscope with a magnification of 1QQ, and the results shown in Table 4 were obtained.

Table 3 in the margin below: Developer prescription sensitivity '''': Optical density 1.50 Reciprocal of exposure maximum (fogging)
(The control is set to 100 and the relative sensitivity is expressed relative to that.) Latex stability: KNOa is compared to polymer latex 4.
Added 0.299 and 0.50 to 0112 and evaluated the aggregation state after standing for 3 hours (visual judgment) A: No change B:
Cloudy C: Coagulated matter present D = Nissurarie Halftone dot quality = 50% The halftone dots were observed and visually graded into A to D.

A: Excellent B: Practically acceptable C: Poor D: Very poor [Scratch strength] After developing, fixing, and rinsing in the above processing steps, the film surface was scratched with a weighted metal needle while immersed in rinsing water. By scratching, the lowest scratch strength of the metal needle (scratching strength) was determined.

As is clear from Table 4 below, the light-sensitive material containing low molecular weight gelatin and polymer latex of the present invention provides almost the same sensitivity in both developers (I) and (II) having different ionic strengths. That is, the dependence on the developer is small. The polymer latex emulsion polymerized using the low molecular weight gelatin of the present invention is stable in the presence of an electrolyte,
Moreover, the change in sensitivity due to its addition is small. In Comparative Examples (1), (1'), (2), (2'), (3) and (3'), the stability of the polymer latex was poor, and the halftone dot quality of lithographic development was also poor. Also, the film surface strength is low.

Claims (1)

[Claims] A method for producing a photographic light-sensitive material comprising coating a photographic constituent layer containing a hydrophilic colloid, characterized in that the photographic constituent layer is coated in the presence of low molecular weight gelatin and polymer latex in the hydrophilic colloid. A method for producing a photographic material.