JPS5833541B2 - A new way of life - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for preventing scratches on photographic materials, and more specifically, to prevent scratches that occur on the surface of photographic materials due to contact, friction, etc. between photographic materials and packaging materials, packaging machines, cameras, processing machines, etc. It concerns a novel method for doing so.

Generally, a photographic light-sensitive material consists of a support and at least one photosensitive layer coated on the support.

-・In silver halide photographic materials, paper, glass,
At least one photosensitive layer is formed by coating a support such as a cellulose acetate film or a polyester film and a photosensitive material, silver halide, on the support. Hydrophilic colloids, especially gelatin, are usually used as binders.

The coated film of a photographic light-sensitive material made of gelatin has a high coefficient of friction against other metal surfaces or gelatin surfaces.For this reason, photographic light-sensitive materials that use hydrophilic colloids, especially gelatin, as a binder generally have a high coefficient of friction when the surface is exposed to contact, friction, etc. It has a serious drawback of being easily scratched.

In particular, silver halide photographic light-sensitive materials are used as photosensitive substances.Because silver halide is sensitive to pressure, scratches caused by contact, friction, etc. can sometimes cause pressure fog, desensitization due to pressure, etc. This causes a fatal effect on photographic images.

For this reason, in silver halide photographic light-sensitive materials, a non-light-sensitive protective layer is usually provided outside the light-sensitive emulsion layer, and silica gel, glass, synthetic resin, etc. are present in the protective layer to roughen the film surface. Methods are being used to reduce the contact area and control the coefficient of friction, to prevent fogging caused by pressure, or to protect photographic materials from scratches.

Furthermore, in recent years, a method of dispersing a high-boiling point solvent, solid paraffin, whale oil, etc. in an aqueous gelatin solution and applying it to a photographic material has become known, for example, as described in U.S. Pat. It is being

Although these methods are effective and each has excellent features, they also have associated drawbacks.

For example, silica gel, glass, synthetic resin, etc. are inferior in terms of preventing scratches, and have the disadvantage of being easily scratched especially when applied to the back surface.

Moreover, when these materials are used in large amounts, the transparency of the photosensitive material is reduced, resulting in a disadvantage that the sharpness of the image is deteriorated.

In addition, retouchability also deteriorates. Furthermore, if a high boiling point solvent, which is also used as a solvent for a protected coupler, is used as a slipping agent, the high boiling point solvent will migrate from the inside of the layer to the surface under conditions of high temperature and high humidity, causing the films to stick together.

In addition, the stability of colloidal dispersions of high-boiling solvents depends on the viscosity of the liquid,
Since it largely depends on the concentration of the activator, it has drawbacks such as difficulty in preparing a dispersion.

Furthermore, solid paraffin has poor dispersibility, and in particular, dispersibility is strongly dependent on temperature, making it difficult to create a stable and uniform dispersion of fine particles. There are disadvantages such as the need to keep the entire container or pipe warm in order to remove the heat.

Furthermore, a method of controlling the slipperiness of photographic materials using a surfactant is known, but the surfactant dissolves into the processing solution during processing, resulting in inconveniences such as foaming of the processing solution. Because of this, there are disadvantages such as the amount used is uniform.

Accordingly, a first object of the present invention is to provide a method for controlling the coefficient of friction on the surface of a photographic material to prevent scratches without causing the disadvantages of matting agents or slipping agents.

Another object of the present invention is to provide a photographic material having excellent surface properties that effectively prevent scratches by controlling the coefficient of friction on the surface.

The present inventor has found that the above object can be achieved in a photographic material in which the outermost layer of the photographic material contains at least one compound selected from the following general formula [I] or [II]. I found it.

[In the formula, R1, R2 and R3 each represent a substituted or unsubstituted alkyl group or aralkyl group having 10 or more carbon atoms.

[In the formula, R4 and R6 are each a substituted or unsubstituted alkyl group or aralkyl group having 10 or more carbon atoms,
-R60COR7 group, or RsCOOR9 group (here, R6 and R8 represent an alkylene group, and R7 and Ro each represent a substituted or unsubstituted alkyl group or aralkyl group having 10 or more carbon atoms).

): X represents two bonding groups selected from an oxygen atom, a sulfur atom and a -5-8- group.

] Next, typical specific examples of the compounds represented by the general formulas C1l and [II] according to the present invention will be listed, but the compounds used in the present invention are not limited thereto.

The compounds represented by [1] and [■] according to the present invention can be directly dispersed in an aqueous phase or a hydrophilic colloid solution, for example, a gelatin solution, either alone or in a mixture of two or more.

The compound according to the present invention can also be dissolved in a high-boiling solvent or a mixture of a high-boiling solvent and a low-boiling solvent, and then dispersed in the aqueous phase or the hydrophilic colloid solution in the presence of a dispersant.

As the dispersant, surfactants commonly used for photography can be used, such as those appropriately selected from anionic surfactants, nonionic surfactants, amphoteric surfactants, and cationic surfactants. using the
Using an ultrasonic homogenizer or a bulb homogenizer, the particles are dispersed to preferably have a particle size of 0.1 to 10μ to create a 0/W type emulsion, and then this dispersion is added to a gelatin solution to form the outermost layer of the photographic light-sensitive material. By containing it in at least one of the protective layer or the backing layer, it is possible to obtain a photographic material that is slippery and resistant to scratches when it comes into contact with packaging materials, packaging machines, cameras, processing machines, etc. .

High boiling point solvents useful in the present invention include, for example, U.S. Pat.
It is described in the specification of No. 027.

Examples of the low boiling point solvent include methanol, ethanol, acetone, ethyl acetate, and ethyl chloride.

Even when these slipping agents according to the present invention are used alone or in combination with a high-boiling point solvent and a low-boiling point solvent, the effect as a slipping agent remains almost the same.

However, the stability of the dispersion itself varies depending on the type of slippery agent used, the combination of high boiling point solvents, etc. used in combination, but in terms of the stability of the dispersion liquid, it is better to use it in combination with high boiling point solvents and low boiling point solvents. It's advantageous.

In this case, it is desirable to remove the low boiling point solvent by heating or reducing pressure after the dispersion is completed.

When these slipping agents are used in a weight ratio of 0.3 to 30% to the water-soluble binder such as gelatin constituting the layer, the surface physical properties of the protective layer and backing layer are particularly favorable. Become.

Although the method of the present invention can be applied to various photographic materials, it can be particularly advantageously applied to photographic materials using a hydrophilic colloid as a binder, such as photographic materials using gelatin as a binder.

In addition to gelatin, hydrophilic colloids advantageously used in the present invention include derivative gelatin colloidal aluminum 7"
Agar, gum arabic, alginic acid, cellulose derivatives such as cellulose acetate hydrolyzed to an acetyl content of 19-26%, acrylamide, imidized polyacrylamide, casein, urethane carboxylic acid groups such as vinyl alcohol-vinyl cyanoacetate copolymer. Also included are vinyl alcohol polymers containing cyanoacetyl groups, hollyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, and polymers obtained by polymerizing proteins or saturated acylated proteins with monomers having vinyl groups.

In the present invention, it is desirable to use various film property improvers, such as hardeners, if necessary, for the purpose of improving the physical properties of the coating film made of the hydrophilic colloid.

For example, if a hardening agent is used in combination, not only will a synergistic effect be obtained in preventing abrasions as referred to in the present invention, but also the mechanical strength of the film and the dissolution resistance to processing liquids will be further improved, resulting in extremely good film properties. You can get the photographic materials you have.

When gelatin is used as a hydrophilic colloid, specific examples of typical hardening agents include aldehyde, epoxy, ethyleneimine, active halogen, vinyl sulfone, incyanate, sulfonic acid ester, and carbodiimide. Examples of hardening agents include hardeners such as A-based hardeners, mucochloric acid-based hardeners, mucochloric acid-based hardeners, and acyloyl-based hardeners.

These gelatin hardening agents that can be applied to the present invention are described, for example, in US Pat. No. 3,539,644 and US Pat.
specification, specification number 2726162, specification number 2816
Specification No. 125, Specification No. 3047394, West German Patent No. 1085663, British Patent No. 1033518, Japanese Patent Publication No. 48-3549, PB Report No. 1
No. 9921, US Pat. No. 2950197, US Pat. No. 2964404, US Pat. No. 2983611, US Pat. No. 3271175, US Pat.
No. 27, No. 2994611, British Patent No. 822061, No. 1049083, No. 1202052, No. 1230354, West German Patent No. 872153, Publication No. 44-29622,
JP 47-25373, JP 47-8736, JP 46-38715, JP 49-73
122, JP 48-74832, JP 49-24435, JP 48-43319, JP 48-43320, JP 49-11
It is described in JP-A-6154, JP-A-50-63061, JP-A-50-62250, JP-A-50-109251, etc.

The amount of hardening agent used at this time may be within any range that does not impair the effects of the present invention, depending on the type of gelatin film desired, required physical properties, and photographic properties. It is desirable that the gelatin derivative is contained in an amount of 0.01% by weight or more, preferably 1% by weight or more of the amount of gelatin in a dry state.

The hydrophilic colloid used in the present invention may optionally contain photographic additives other than the hardening agent, such as gelatin plasticizers, surfactants, ultraviolet absorbers, anti-staining agents, etc.
PH regulator, antioxidant, antistatic agent, thickener, graininess improver, dye, mordant, brightener, development speed regulator,
Matting agents and the like can be used within a range that does not impair the effects of the present invention.

Among the various additives mentioned above, those that can be particularly preferably used in the present invention include, for example, thickeners and plasticizers described in US Pat.
Publication No. 9, West German Patent No. 1904604, Japanese Unexamined Patent Publication No. 4
No. 8-63715, Japanese Patent Publication No. 45-15462, Belgian Patent No. 762833, US Patent No. 3767410, Belgian Patent No. 55814
Substances described in Specification No. 3, especially styrene maleic acid Nogu copolymer, dextran sulfate, etc.
As the ultraviolet absorber, for example, Japanese Patent Publication No. 48-736, Japanese Patent Publication No. 48-5496, Japanese Patent Publication No. 48-415
72 Publication, Special Publication No. 48-30492, Special Publication No. 4
8-31255, US Pat. No. 3,253,921 and British Patent No. 1,309,349, in particular 2-(2'-hydroxy5'-tert-butylphenyl)benzotriazole, 2-(2 '-Hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-phthyl-5'-butylphenyl)5-chlorobenzotriazole, 2-(2 '-Hydroxy-3',5'-di-tert-butylphenyl) 5-chlorobenzotriazole, etc., as surfactants, British Patent No. 548532, British Patent No. 1216389, US Patent No. 3026
202 specification, U.S. Patent No. 3514293, Japanese Patent Publication No. 44-26580, Japanese Patent Publication No. 17922-1972, Japanese Patent Publication No. 43-17
No. 926, Japanese Patent Publication No. 43-13166, Japanese Patent Publication No. 48-20785, French Patent No. 202588, Belgian Patent No. 773459, Japanese Unexamined Patent Publication No. 1973 (01118), etc. Compounds that contain
In particular, anti-staining agents such as ndium di-2-ethylhexyl sulfosuccinate, ndium-amyludecyl sulfosuccinate, dodecylbenzenesulfonate, triisopropylnaphthalene sulfonate, etc. are described in US Pat. Nos. 2,360,210 and 2,728,659. Compounds described in the specification, Specification No. 2732300, Specification No. 3700453, etc., especially 2-methyl-5-
Hexadecyl-hydroquinone, 2-methyl-5-5
ee-octadecyl-hydroquinone, 2,5-di-t
- Octylhydroquinone and other antistatic agents are disclosed in Japanese Patent Publication No. 46-24159, Japanese Patent Application Laid-Open No. 48-89979, U.S. Pat. No. 2,882,157, and U.S. Pat.
Specification No. 2535, JP-A-48-20785, JP-A-48-43130, JP-A-48-90391
Publication No. 46-39312, Special Publication No. 48-
Compounds described in JP 43809, JP 49-4853, JP 49-64, JP 47-8742, JP 4733627, etc.
Examples of matting agents include compounds described in British Patent No. 1,221,980, US Pat. No. 2,992,101, and US Pat. Examples include polymers of polymethyl methacrylate having a particle size of 5 to 20 microns.

Supports used in the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper,
Typical examples include glass plates, cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, polycarbonate films, polystyrene films, etc., and these supports are used in photographic materials. It is selected as appropriate depending on the purpose.

The method of the present invention can be applied to various photographic materials having a hydrophilic colloid layer, but typically photographic materials using rogen silver as a photosensitive component, such as general negative photosensitive materials, general reversal photosensitive materials, etc. It can be used in general positive light-sensitive materials, direct positive light-sensitive materials, special purpose (for example, printing, X-ray, high resolution, infrared, ultraviolet, etc.) silver halide photographic materials, etc.

The present invention will be specifically illustrated below by giving test examples and examples, but the present invention is not limited by these examples.

Test example A dispersion of a slippery agent was prepared as shown below.

Liquids A and B were mixed and emulsified at a pressure of 250 kg/c4 using a valve-type homogenizer manufactured by Manton-Gaulin to obtain an O/W type differential dispersion.

At this time, the particle size of the dispersion in the gelatin aqueous solution was controlled to be about 0.8 μm.

Add liquid C to the obtained dispersion, add water and make 80rIl.
l! It was finished to make a slippery dispersion.

10 CC of each of these dispersions was placed in a test tube at 50°C.
5EP- manufactured by Japan Precision Optical Co., Ltd.
Turbidity was measured using PL.

The results are summarized in Table 1.

As is clear from Table 1, the dispersions containing the slipping agent according to the present invention (A7-19) have better dispersibility and stability than the slipping agent dispersions (Al-6) other than the slipping agent of the present invention. It can be seen that it is in good condition.

Example 1 70CC of a slippery agent dispersion prepared in the same manner as in the test example was prepared as a coating liquid using the following formulation.

On the other hand, one side of the transparent polyethylene terephthalate film base was undercoated, and 7 mo1 of silver iodide was applied on top of it.
A silver iodobromide photographic emulsion containing % yen was coated, and the above coating solution was further coated thereon as a protective layer, and dried to obtain a sample and a light-sensitive material.

For comparison, in addition to the slippery agent used in Test Example 1, a silica gel matting agent 0.5S' and a polymethyl methacrylate matting agent 0.51 were used as matting agents to prepare a comparative photosensitive material.

The friction coefficient and the minimum load at which scratches occur were measured for the photographic material thus obtained.

The coefficient of friction was measured in accordance with the American ASTM method, D-1814, and was expressed as a coefficient of dynamic friction against light-shielding paper for photographic film.

The load at which scratches occur can be measured by continuously applying a load to a needle with a needle head diameter of 0.1 and scratching the surface of the film.
The minimum load at which an abrasion occurred was measured.

The results are summarized in Table 2.

As is clear from Table 2, the samples according to the present invention (A10~
It can be seen that Sample No. 22) has a smaller coefficient of friction than the comparative samples (A1 to A9), and has an excellent effect of reducing scratches.

In addition, the clarity of the sample after processing is also excellent.
It was found that there was no adverse effect on photographic characteristics (sensitivity, cuffing, gradation).

Example 2 A slippery agent dispersion was prepared according to the following formulation.

8 Additives include 2(2'-hydroxy-5'-tert-butylphenyl)penztriazole;2-(2'-hydroxy-3'·5'-di-tert-butylphenyl)penztriazole;Triazole; 2
-(2'-hydroxy-3'-tert-butyl-5'
-phenyl)-5-chloropenttriazole; 2-
(2'-Hydroxy-3'・5'-G-tert-7
"f-ruphenyl)-5-chloropenttriazole 1"
:1:1:1 mixture or 2,5-di-tert-octylhydroquinone was used as antifouling agent.

Solutions A and B were mixed in the same manner as in the test example, and this was added to Solution C to obtain a slippery agent dispersion.

70 cc of this slippery agent dispersion was taken and prepared as a coating liquid using the following formulation.

Prescription One side of the cellulose triacetate film base is undercoated, an antihalation agent is applied on it, and then cyan coupler and silver iodide 10mol1 are applied on top of it in this order.
A red-sensitive layer containing a silver iodobromide emulsion containing a magenta coupler and a silver iodobromide emulsion containing 10 mo1% of silver iodide, a yellow coupler and a silver iodobromide emulsion containing 10 mo1% of silver iodide.
The above solution was applied onto a silver halide multilayer color photographic material coated with a blue-sensitive layer containing a silver iodobromide emulsion containing a silver iodobromide emulsion to obtain a sample photosensitive material as shown in Table 3.

For comparison, 3. only the amount of activator was increased without using liquid A or matting agent. A sample containing Ov was prepared.

The friction coefficients of these sample photosensitive materials were measured in the same manner as in Example 1, and the samples were immersed in a carbonate aqueous solution adjusted to pH 11.0 for 20 minutes at 40°C, and then heated at 40°C.
After washing with running water for 20 minutes and drying, the coefficient of friction was measured.

The results are summarized in Table 3.

It can be seen that the number similarity effect hardly changes.

We also tested the effects on photographic properties, but no changes were observed due to the addition of the slip agent.

Claims (1)

[Scope of Claims] 1. The outermost layer of a photographic material consisting of a support and at least one hydrophilic colloid layer has the following general formula [1] or [ID
1. A method for preventing scratches on a photographic material, which comprises adding at least one compound selected from the following compounds. General Formula [1] [In the formula, R1, R2 and R3 each represent a substituted or unsubstituted alkyl group or aralkyl group having 10 or more carbon atoms. ] General formula [■] [In the formula, R4 and R6 are each a substituted or unsubstituted alkyl group or aralkyl group having 10 or more carbon atoms,
-R60COR7 group or R8COOR9 group (where R6 and R8 represent an alkylene group, and R7 and R9 each represent a substituted or unsubstituted alkyl group or aralkyl group having 10 or more carbon atoms); X is an oxygen atom, a sulfur atom represents a divalent bonding group selected from -8-8- and -8-8- groups. ].