JPH0619519B2 - Photosensitive material having improved transferability of organopolysiloxane - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photographic light-sensitive material containing an organopolysiloxane, and more particularly to a silver halide photographic light-sensitive material containing an organopolysiloxane in a stable manner.

[Background of the Invention]

The silver halide photographic light-sensitive material comprises a support such as paper, glass, cellulose acetate film, polyester film and at least one light-sensitive layer coated on the support. Usually, hydrophilic colloid, especially gelatin is used.

A coating film using this gelatin as a binder has a high coefficient of friction against other metal surfaces or gelatin surfaces. Therefore, photographic light-sensitive materials that use hydrophilic colloids, especially gelatin as a binder, are not susceptible to scratches due to contact or friction on the surface. Since silver halide used as a photosensitive material is sensitive to pressure, scratches due to contact, friction, etc. sometimes cause pressure fog and desensitization due to pressure, which is fatal to photographic images. Influence.

Therefore, in a silver halide photographic light-sensitive material, a non-light-sensitive protective layer is usually provided outside the light-sensitive emulsion layer, and silica gel, glass, synthetic resin, etc. are allowed to exist in the protective layer to roughen the film surface. Means for controlling the friction coefficient, preventing fogging due to pressure, or protecting the photographic light-sensitive material from scratches by surfaceizing and reducing the contact area are adopted. In recent years, a method of dispersing a high-boiling solvent, solid paraffin, whale oil, etc. in an aqueous gelatin solution and applying it to a photographic light-sensitive material is known from, for example, U.S. Pat.No. 3,121,060 or JP-A-49-5017. ing.

These are effective methods, each of which has excellent characteristics, but has disadvantages associated therewith. For example, silica gel, glass, or synthetic resin is inferior in terms of preventing scratches, and if a large amount of these is used, the transparency of the light-sensitive material is lowered and, as a result, the sharpness of the image is deteriorated. ing.

Further, when a high boiling point solvent which is also used as a solvent for a protect type coupler is used as a slip agent, the high boiling point solvent is transferred from the layer to the surface under the condition of high temperature and high humidity, and the film members cause adhesion. Further, the stability of a colloidal dispersion of a high boiling point solvent depends largely on the viscosity of the solution, the concentration of the activator, etc., and thus there are drawbacks such as difficulty in preparing the dispersion.

Furthermore, since solid paraffin has poor dispersibility, and particularly the dispersibility strongly depends on temperature, it is difficult to form a stable and uniform fine particle dispersion, and solid paraffin easily adheres to the wall of a container or piping. In order to remove this, there is a drawback that the container or the entire pipe must be kept warm.

Furthermore, a method of controlling the slip property of a light-sensitive material using a surfactant is also known, but there is a problem that the surfactant is eluted into the processing solution during processing, resulting in foaming of the processing solution. As a result, there is a drawback that the amount used is limited.

In particular, fluorine-containing surfactants tend to stick as dry deposits on the transport rollers inside the processor when they elute into the processing liquid,
This causes inconvenience such as uneven development due to roller contamination.

Also known is a method of incorporating a liquid organopolysiloxane into a photographic emulsion layer, a protective layer or a back layer to make the surface of the light-sensitive material slippery. For example, U.S. Pat.
A method of combining dimethyl silicone with a particular surfactant as described in US Pat. No. 3,080,31.
A method using a mixture of dimethyl silicone and diphenyl silicone as described in U.S. Pat.
Methods using triphenyl-terminated methylphenyl silicones as described in 3,118, U.S. Pat.
A method using a di-lower alkyl silicone and a specific surfactant as described in 9,567, and a method using a polysiloxane having a long chain alkyl group in the side chain as described in JP-B-53-292. , A method using a polysiloxane having a polyoxyethylene group in the side chain as described in JP-B-55-92843, and a silicone polymer and a cationic system as described in JP-A-49-125015. A method using a fluorosurfactant, a method using a polysiloxane having a special functional group as described in JP-A-60-140341, JP-A-60-140342 and JP-A-60-140343. Are known.

Although these compounds improve the slipperiness of the light-sensitive material, they must be contained in a large amount in order to obtain sufficient slipperiness. However, when used in a large amount, when it comes into contact with another object, the organopolysiloxane is transferred to the contacted other object, and if this occurs in the manufacturing process, there is a problem that a transport failure occurs and a defective product occurs.

The inventors of the present invention have made earnest studies to solve the above problems, and as a result, when the hardness of the organopolysiloxane-containing layer is increased, the transfer is reduced, and when the hardness of the silver halide emulsion layer is increased to the same degree. The inventors have found that sensitivity is deteriorated and have reached the present invention.

[Object of the Invention]

An object of the present invention is, firstly, to provide a silver halide photographic light-sensitive material which does not cause transfer failure even if a large amount of polyorganosiloxane is added, and secondly, a large amount of polyorganosiloxane is added. Another object of the present invention is to provide a silver halide photographic light-sensitive material that does not transfer even if added and does not affect photographic performance.

[Structure of Invention]

An object of the present invention is to provide a photographic light-sensitive material having at least one hydrophilic colloid layer on the outermost surface on a support, wherein at least one of the outermost hydrophilic colloid layers contains an organopolysiloxane, and gelatin. A photographic light-sensitive material characterized by being hardened by a high-molecular hardener which is a compound having a molecular weight (number average molecular weight) of 3000 or more and having at least two hardening groups for reacting in the same molecule. Achieved by

Hereinafter, the present invention will be described in detail.

The organopolysiloxanes used in the present invention include U.S. Pat.
3,042,522, 3,080,317, 2,694,637, Japanese Patent Sho3
9-15714, British Patents 1,030,811, 1,143,118,
1,528,656, 1,275,657, 1,278,402, 1,31
No. 3,384, Japanese Patent Publication No. 51-15740, Japanese Patent Publication No. 45-34230, No. 46-
27428, JP-A-49-62128, JP-B-49-62127, JP-B-53-292, JP-B-55-49294, JP-A-60-140341,
60-140342, 60-140343, 60-188945, 60-
231704, 60-231720, 60-240761, 60-24316
No. 7, No. 60-240732, No. 60-245638, No. 61-216, No. 6
The compounds described in Nos. 1-232 and 61-260 are included.

Among these organopolysiloxanes, preferred are those having a structural unit represented by the following general formula [I].

General formula [I] Here, R ₁ represents a hydrogen atom, a hydroxyl group or an organic group, and R ₂ represents an organic group.

The organic group of R ₁ and R ₂ is an alkyl group (preferably having a carbon number of 1 to 18), a substituted alkyl group (for example, carboxyalkyl, aminoalkyl, alkylaminoalkyl, mercaptoalkyl, alkoxyalkyl, glycidyloxyalkyl, aralkyl) , _{aryloxyalkyl, -R 3 -R 4 -R 5 (} R 3 is an alkylene group, R ₄ is 2 or more linked group of the oxyalkylene group, R ₅ represents an alkyl group.), etc.}, an alkenyl group (Eg vinyl, allyl etc.), alkoxy group (eg methoxy, ethoxy etc.),
Included are aromatic groups (eg, phenyl), and groups that include these groups.

Further, the end of the organopolysiloxane has the following general formula [I
Those having a structural unit represented by I] are preferable.

General formula (II) Here, R ₆ , R ₇ and R ₈ each represent a hydrogen atom, a hydroxyl group or an organic group, and as the organic group, R ₁ and
The examples of the organic group for R ₂ are mentioned.

The organopolysiloxane used in the present invention is not particularly limited in viscosity, but the viscosity measured at 25 ° C. is usually 20
A value in the range of up to 100,000 centistokes is suitable.

The molecular weight of the polysiloxane according to the present invention is 100 to 10
The range of 00000 is suitable and can be used according to the purpose, but the range of 2000 to 50,000 is preferable.

Next, specific compounds that can be used in the present invention are listed, but the compounds used in the present invention are not limited thereto.

S-1 S-2 S-3 S-4 S-5 S-6 S-7 S-8 S-9 S-10 S-11 S-12 S-13 S-14 S-15 S-16 S-17 S-18 S-19 S-20 S-21 S-22 S-23 S-24 S-25 S-26 S-27 S-28 S-29 S-30 S-31 S-32 S-33 S-34 S-35 S-36 S-37 S-38 S-39 S-40 S-41 S-42 S-43 S-44 S-45 S-46 S-47 The organopolysiloxane used in the present invention is preferably contained in the hydrophilic colloid of the outermost hydrophilic colloid layer in an amount of 0.3 to 30% by weight.

The polymeric hardener in the present invention means a compound having a molecular weight (number average molecular weight) of 3,000 or more, which has at least two hardener groups for reacting with gelatin in the same molecule.

Here, as a dura mater for reacting with gelatin etc.,
For example, there are an aldehyde group, an epoxy group, an active halide group (such as dichlorotriazine), an active vinyl group and an active ester group.

The number of these groups may be at least 2 in the polymer hardener, but is preferably 10 to 5000. Further, those having a molecular weight of about 3000 to 500,000 are preferably used.

Generally, the polymer part having a hardening group for reacting with gelatin is preferably hydrophilic, but even if it is not hydrophilic, it is emulsified and dispersed in a hydrophilic colloid (eg gelatin) (if necessary, an organic solvent is used). It can also be used by dispersing.

Examples of the polymer hardener used in the present invention include dialdehyde starch, polyacrolein, and U.S. Pat. No. 3,396,029.
Polymers having aldehyde groups such as acrolein copolymers described in No. 3, U.S. Pat.No. 3,623,878 epoxy-containing polymers, U.S. Pat.No. 3,362,827, Research Disclosure 17333 (1978) dichloro, etc. Polymers having a triazinyl group, polymers having an active ester group described in JP-A-56-66841, JP-A-56-142524, US Pat. No. 4,161,407
JP-A-54-65033, Research Disclosure Magazine 16725 (1978), and the like, and polymers having an active vinyl group or a group serving as a precursor thereof. It is preferable to use a polymer having a base group, and particularly, as described in JP-A-56-142524, an active vinyl group or a precursor group thereof is bonded to the polymer main chain by a long spacer. Polymers are particularly preferred.

Specific examples of the polymer hardener used in the present invention are shown below.

HP-1 HP-2 HP-3 HP-4 HP-5 HP-6 HP-7 HP-8 HP-9 HP-10 HP-11 HP-12 HP-13 HP-14 HP-15 HP-16 HP-17 HP-18 HP-19 HP-20 HP-21 HP-22 HP-23 HP-24 HP-25 HP-26 HP-27 HP-28 As the polymer hardener of the present invention, it is possible to use a polymer having at least two hardener groups in the same molecule for reacting with gelatin from the beginning, such as the polymer described above. However, a polymeric hardener in a hydrophilic colloid layer coated using a gelatin hardener and a polymer which reacts with it to give a polymer having at least two hardener groups in the same molecule. To achieve the objects of the present invention.

Thus, as a gelatin hardener used to make a polymeric hardener in a hydrophilic colloid layer, a low-molecular hardener, such as "The Theory to the Photo" by TH James.
The low molecular hardeners described in "Graphic Process", 4th edition, pp. 77 to 84 are used, and among them, low molecular hardeners having a vinyl sulfone group or a triazine ring are preferable, and particularly, JP-A-53-53 The hardeners described in 41221 and 60-225143 are preferred.

Specific examples of the gelatin hardener of the present invention which gives the polymer hardener are shown below.

_{H-1 (CH 2 = CHSO} 2 CH 2 CONHCH) 2 H-2 (CH 2 = CHSO 2 CH 2 CONHCH 2) 2 -CH 2 H-3 _{H-4 CH 2 = CH-} CHSO 2 -CH = CH 2 H-5 CH 2 = CHSO 2 CH 2 OCH 2 -SO 2 -CH = CH 2 H-6 CH 2 = CHSO 2 CH 2 CH ₂ CH ₂ SO ₂ CH = CH ₂ H-7 H-8 H-9 Formalin H-10 H-11 H-12 H-13 _{H-14 CH 2 = CHSO 2} CH 2 CH 2 SO 2 CH = CH 2 H-15 H-16 H-17 H-18 H-19 H-20 H-21 Also, the polymer used to make the polymeric hardener in the hydrophilic colloid layer must have at least two nucleophilic groups that react with the gelatin hardener in the same molecule. , For example, polymers having a primary amino group described in British Patent No. 2,011,912, polymers having a sulfinic acid group described in JP-A-56-4141, US Pat.
Examples thereof include polymers having a phenolic hydroxyl group described in 4,207,109 and polymers having an active methylene group described in US Pat. No. 4,215,1956.

Specific examples of the polymer that provides the polymeric hardener used in the present invention are shown below.

Q-1 Q-2 Q-3 Q-4 Q-5 Q-6 Q-7 Q-8 Q-9 The method for synthesizing the polymeric hardener used in the present invention is shown below.

Synthesis Example 1 Synthesis of N- (3- (chloroethylsulfonyl) propioyl) aminomethylacrylamide In the reaction vessel of 2, distilled water 1400 ml, sodium sulfite 22
4 g and 220 g of sodium hydrogencarbonate were added, dissolved with stirring, cooled to 5 ° C., and 260 g of chloroethanesulfonyl chloride was added dropwise over about 1 hour and 30 minutes. After dripping 49
% Sulfuric acid (160 g) was added, and the precipitated crystals were filtered and washed with 400 ml of distilled water. The filtrate and the washing solution were added to the reaction vessel of 3, and 246 g of methylenebisacrylamide dissolved in 480 ml of distilled water and 1480 ml of ethanol was added dropwise at 5 ° C. for about 30 minutes. After leaving the reaction sample in the refrigerator for 5 days to complete the reaction, the precipitated crystal was collected by filtration, washed with 800 ml of cooled distilled water, and recrystallized from 2000 ml of 50% ethanol aqueous solution.
210 g of white powder was obtained. The yield is 49%.
mp was 192 ° C or higher (decomposition).

Synthesis Example 2 Synthesis of N- (2- (chloroethylsulfonyl) acetyl) aminomethylacrylamide To the reaction solution of 1, 720 ml of methanol and 80.0 g of N-methylolacrylamide were added, and concentrated hydrochloric acid was added with stirring at room temperature.
After adding 40 ml and stirring for 16 hours, 0.4 g of hydroquinone monomethyl ether was added, and methanol was distilled off with an evaporator. Chloroethanesulfonylacetamide (100 g), hydroquinone monomethyl ether (0.32 g) and p-toluenesulfonic acid (0.22 g) were added to the remaining 62.4 g of oil, and the mixture was heated to 150 ° C. to distill off the produced CH ₃ OH.

The reaction was completed in about 15 minutes, and the remaining crystals were recrystallized from 250 ml of 50% aqueous ethanol solution to obtain 61 g of white powder.
The yield was 42%.

Synthesis Example 3 Poly-N- {3- (vinylsulfonyl) propioyl} aminomethylacrylamide-co-acrylamido-2-methylpropanesulfonate sodium (HP-3) In a reaction solution of 200 ml, 5.65 g of the monomer of Synthesis Example 1, Acrylamide-2-methylpropanesulfonic acid sodium 9.16
g, 80 ml of 50% aqueous ethanol solution was added, and the mixture was stirred and dissolved. The temperature was raised to 80 ° C while passing nitrogen gas, and 0.1 g of 2,
Add 2'-azobis (2,4-dimethylvaleronitrile),
After 30 minutes, the same amount was added, and heating and stirring were continued for 1 hour. Then, cool to 10 ° C and add 2.5g triethylamine mixed with 80ml ethanol,
Stirring was continued for 1 hour, the reaction sample was added to 1 of acetone, and the formed precipitate was collected by filtration and vacuum dried to obtain 12.4 g of a white polymer. The yield was 85%, the intrinsic viscosity [η] of this polymer was 0.227, and the vinyl sulfone content was 0.95 × 10 ^3.
It was equivalent / g polymer.

▲ ▼ ＝ 7200 Synthesis Example 4 Poly-N- {2- (vinylsulfonyl) acetyl} aminomethylacrylamide-co-acrylamide
(HP-7) To a 3000 ml reaction vessel, 53.7 g of the monomer of Synthesis Example 2, 163.3 g of acrylamide and 1955 g of methanol were added and dissolved by stirring, and the temperature was raised to 60 ° C. while passing nitrogen gas.
After adding 2 g of 2,2'-azobis (2,4-dimethylvaleronitrile) and heating for 4 hours, the mixture was cooled to room temperature, 20.2 g of triethylamine was added, the mixture was stirred for 2 hours, and the precipitate was collected by filtration. After vacuum drying, 194.3 g of a white polymer was obtained.
The yield is 92.7%, and the vinyl sulfone content of this polymer is
0.50 × 10 ³ equivalent / g polymer. ▲ ▼ ＝ 4900 Synthesis Example 5 Potassium poly-vinylbenzenesulfinate-sodium co-acrylamido-2-methylpropanesulfonate
(Q-1) To a 500 ml reaction vessel, 45.8 g of sodium acrylamido-2-methylpropanesulfonic acid, 20.6 g of potassium vinylbenzenesulfinate, 180 ml of ethanol and distilled water were added, and heated to 75 ° C. with stirring, ( 2,2'-Azobis- (2-amine) propane) dihydrochloride (0.82 g) was added and the mixture was heated for 4 hours, allowed to cool to room temperature, ethanol 72 ml, distilled water 27
8 ml was added and filtered to obtain a colorless transparent viscous liquid.

The viscosity of this polymer solution at 25 ° C. was 3.25 cp, the solid content concentration was 10.3 WT%, and the sulfinic acid content was 6.2 × 10 ^-6 equivalent /
It was g. ▲ ▼ = 16000 Other polymer hardeners can also be easily synthesized based on these synthetic examples or the methods described in the above patent specifications. Also, some compounds are commercially available.

When the polymer hardener of the present invention is used, the amount used can be arbitrarily selected according to the purpose. Normally, 100 x dry gelatin has 0.5 x 10 functional groups that react with gelatin.
A polymeric hardener corresponding to a range of ^-3 equivalent to 5 x 10 ^-2 equivalent is used. Particularly preferred is the range from 0.5 × 10 ⁻³ equivalent to 2 × 10 ⁻² equivalent.

As a hardener for the outermost hydrophilic colloid layer (hereinafter referred to as the outermost surface layer of the present invention) containing the organopolysiloxane according to the present invention and hardened with a polymer hardener, In addition to using a molecular hardener alone, JP-A-51-7
8788, 53-41221, 60-225143, U.S. Pat.
25,287, 3,945,853, JP-A-59-31944, 55-
Other low molecular hardeners described in No. 736 (▲ ▼ <3000)
Can be used in combination, and in the present invention, it is preferable to use in combination. Hardeners that can be used in combination include compounds having a reactive halogen atom such as 2-hydroxy-4,6-dichloro-1,3,5-triazine, and compounds having a reactive olefin such as divinyl sulfone. , Isocyanates, aziridine compounds, epoxy compounds, mucochloric acid, chrome alum, and aldehydes, specifically, the above-mentioned H-1.
To H-21.

In order to suppress the transfer of the organopolysiloxane, the outermost surface layer of the present invention is preferably hardened to have a swelling degree of 1.0 to 5.0, particularly 1.5 to 3.0, while the photographic photosensitive layer is a silver halide emulsion layer. From the viewpoint of desensitization, it is preferable to harden the film within the range of 1.5 to 10, particularly 2 to 7. Here, the degree of swelling is a value measured as follows.

Measurement of swelling degree: The sample is dipped in a developing solution at 38 ° C. and swelled for 30 seconds, which is represented by X in the following equation.

X = (film thickness increased by swelling) / (film thickness when dried) The outermost surface layer of the present invention contains an organopolysiloxane,
In addition to being hardened by a polymer hardener, it may have a constitution known as a protective layer of a usual silver halide photographic light-sensitive material. The thickness of the outermost layer is suitably in the range of 0.1 to 5.0 μm, preferably 0.3 to 1.5 μm.

In order to contain the organosiloxane used in the present invention in the outermost surface layer of the present invention and harden it with a polymer hardener, a method of adding both of them to the coating solution in advance, A polymer that provides a molecular hardener is added to the outermost surface layer to allow overcoating or penetration of an organopolysiloxane or an organopolysiloxane and a hardener that reacts with the polymer to form a polymeric hardener. Although there are methods, a method of adding both of them to the coating solution in advance is preferable from the viewpoint of manufacturing cost and effect.

As a method for adding to the coating liquid, both are dispersed in water or a hydrophilic colloid solution such as a gelatin solution in the presence of a dispersant, and further added to a desired coating liquid, or both are directly added to the coating liquid. There is a method of dispersing and applying.

As the dispersant for the organosiloxane, a surfactant usually used for photography can be used. For example, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant or a cationic surfactant is appropriately used. Depending on what is selected, it can be dispersed using an ultrasonic homogenizer or a valve homogenizer. The preferable particle size is in the range of 0.05 to 10 μm. If the particle size exceeds this range and the particle size is too small, the effect of the present invention, particularly the slipperiness is deteriorated, and if it is too large, devitrification occurs and this is not preferable as a light-sensitive material.

It is advantageous to use gelatin as the hydrophilic colloid contained in the outermost surface layer of the present invention and the hydrophilic colloid of the other hydrophilic colloid layers of the photographic light-sensitive material of the present invention. , 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 copolymers or Use a vinyl alcohol polymer containing a cyanoacetyl group, polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, a polymer obtained by polymerizing a protein or a saturated acylated protein with a monomer having a vinyl group, and the like. be able to.

In the present invention, it is desirable to use various film physical property improving agents, for example, hardeners, if necessary, for the purpose of improving the physical properties of the hydrophilic colloid layer.

When gelatin is used as the hydrophilic colloid, typical hardeners include aldehyde type, epoxy type, ethyleneimine type, active halogen type, vinyl sulfone type,
Examples include isocyanate-based, sulfonate-based, carbodiimide-based, mucochloric acid-based, and acyloyl-based hardening agents.

These gelatin hardeners are described, for example, in U.S. Pat.
No. 4, No. 3,642,486, No. 2,726,162, No. 2,816,1
No. 25, No. 3,047,394, West German Patent No. 1,085,663, British Patent No. 1,033,518, Japanese Patent Publication No. 48-3549, PB Report No.
No. 19921, U.S. Pat.Nos. 2,950,197 and 2,964,404,
No. 2,983,611, No. 3,271,175, No. 2,938,892
No. 3, No. 3,640,720, No. 3,058,827, No. 2,994,61
1, British Patent Nos. 822,061, 1,042,083, 1,2
02,052, 1,230,354, West German Patent 872,153,
JP-B-44-29622, JP-B-47-25373, JP-B-47-8736,
JP-B-46-38715, JP-A-49-73122, JP-A-48-74832
JP-A-49-24435, JP-A-48-43319, JP-A-48-4
No. 3320, JP-A-49-116154, Japanese Patent Application No. 48-112325, Japanese Patent Application No. 48-110996, Japanese Patent Application No. 49-15096 and the like.

The amount of the hardener may be in any range that does not impair the effects of the present invention depending on the type of the intended gelatin film, the required physical properties, and the photographic properties. It is desirable that the content in the dry state is 0.01% by weight or more, preferably 1% by weight or more.

In the hydrophilic colloid layer of the photographic light-sensitive material of the present invention, if necessary, as a photographic additive other than the hardener, for example, gelatin plasticizer, surfactant, ultraviolet absorber, antistaining agent, pH adjusting agent, Antioxidants, antistatic agents, thickeners, graininess improvers, dyes, modulants, whitening agents, development speed regulators, 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 described above, those that can be particularly preferably used in the present invention include, for example, as a thickener or a plasticizer, U.S. Patent 2,960,404, Japanese Patent Publication No. 43-4939, West German Patent 1,90.
4,604, JP-A-48-63715, JP-B-45-15462, Belgium Patent No. 762,833, U.S. Patent No. 3,767,410, Belgium Patent No. 588,143, especially styrene-sodium maleate. Examples of ultraviolet absorbers such as copolymers and dextran sulphate include, for example, Japanese Patent Publication
48-736, JP-B-48-5496, JP-B-48-41572, JP-B-48-30492, JP-B-48-31255, U.S. Pat.No. 3,253,92
1, compounds described in British Patent 1,309,349,
In particular, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-butylphenyl) -5-chlorobenzotriazole, 2- (2'- Hydroxy-3 ', 5'-di-tert
-Butylphenyl) -5-chlorobenzenetriazole and the like, as surfactants, British Patent No. 548,532, British Patent No. 1,216,389, US Patent No. 3,026,202, US Patent No.
3,514,293, Japanese Patent Publication No.44-26580, Japanese Patent Publication No.43-17922,
Japanese Patent Publication 43-17926, Japanese Publication 43-13166, Japanese Publication 48-20785
Compounds, French Patent No. 202,585, Belgian Patent No. 773,459, etc., especially sodium-di-2-ethylhexyl sulfosuccinate, sodium-amyl-
Decyl sulfosuccinate, sodium dodecyl benzene sulfonate, sodium triisopropyl naphthalene sulfonate, etc., as an antistain agent, for example, U.S. Patent Nos. 2,360,210, 2,728,659, 2,732,300,
Compounds described in No. 3,700,453, etc., especially 2-methyl-5-hexadecyl-hydroquinone, 2-methyl-
5-sec-octadecyl-hydroquinone, 2,5-di-tert-octylhydroquinone, etc., as an antistatic agent, JP-B-46-24159, JP-A-48-89979, U.S. Pat.
882,157, 2,972,535, JP-A-48-20785, JP-A-48-43130, JP-A-48-90391, JP-B-46-39312,
Japanese Patent Publication 48-43809, Japanese Publication 49-4853, Japanese Publication 49-64,
Compounds described in JP-B-47-8742, JP-A-47-33627 and the like, and as a matting agent, for example, U.S. Pat.No. 1,221,980,
The compounds described in US Pat. Nos. 2,992,101 and 2,956,884, particularly silica gel having a particle size of 0.5 to 20 μm, a polymer of polymethylmethacrylate having a particle size of 0.5 to 20 μm, and the like can be mentioned.

As the support used in the photographic light-sensitive material of the present invention, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, polyester film such as polyethylene terephthalate, polyamide film,
Polypropylene film, polycarbonate film,
A polystyrene film or the like is typically included, and each of these supports is appropriately selected according to the purpose of use of the light-sensitive material.

The present invention relates to various silver halide photographic light-sensitive materials having an outermost surface layer of a hydrophilic colloid layer, for example, a general negative light-sensitive material, a general reversal light-sensitive material, a general positive light-sensitive material, a direct positive light-sensitive material, special (for printing, for example, X-ray, high resolution, infrared, ultraviolet, etc.) silver halide photographic light-sensitive materials and the like.

〔Example〕

Specific examples of the present invention will be described below, but embodiments of the present invention are not limited to these.

In all of the following examples, the addition amount in the silver halide photographic light-sensitive material is per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver.

Example 1 On a triacetyl cellulose film support, each layer having the following composition was sequentially formed from the support side to prepare a multilayer color light-sensitive material sample 1-NO.1.

First layer: antihalation layer A gelatin layer containing black colloidal silver.

Gelatin 2.2 g / m ² Second layer; Intermediate layer Gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Gelatin 1.2 g / m ² 3rd layer; low-sensitivity red-sensitive silver halide emulsion layer Monodisperse emulsion (Emulsion I) consisting of AgBrI containing 0.30 μm average grain size and 6.0 mol% AgI ... Silver coating amount 1.8 g / m ² Sensitizing dye I ... 6 × 10 ⁵ mol per mol of silver Sensitizing dye II: 1.0 × 10 ⁵ mol per mol of silver Cyan coupler (C-1) ... 0.06 mol per mol of silver Colored cyan Coupler (CC-1) ... 0.003 mol per mol of silver DIR compound (D-1) ... 0.0015 mol per mol of silver DIR compound (D-2) ... 0.002 mol per mol of silver Gelatin 1.4 g / m ² 4th layer: high-sensitivity red-sensitive silver halide emulsion layer Monodisperse emulsion (Emulsion II) consisting of AgBrI containing 0.5 μm average grain size and 7.0 mol% AgI ... Silver coating amount 1.3 g / m ² sensitizing dye I ... silver mol per 3 × 10 ^-5 mol sensitizing dye II ... 1 mol of silver relative to 1.0 × 10 ^-5 mol cyan coupler (C-1) ... silver model 0.02 mol colored cyan coupler (CC-1) ... 0.0015 mol DIR compound per mol of silver (D-2) ... 0.001 mol of gelatin 1.0 / m ² Layer 5 per mol of silver relative; intermediate layer first Same as 2 layers, gelatin layer.

Gelatin 1.0 g / m ² 6th layer; low-sensitivity green-sensitive silver halide emulsion layer Emulsion-I ... Coated silver amount 1.5 g / m ² Sensitizing dye III ... 2.5 × 10 ^-5 mol sensitized per 1 mol silver Dye IV: 1.2 × 10 ⁻⁵ mol per mol of silver Magenta coupler (M-1): 0.050 mol per mol of silver Colored magenta coupler (CM-1): 0.009 mol per mol of silver DIR compound (D-1) ... 0.0010 mol per 1 mol of silver DIR compound (D-3) ... 0.0030 mol per 1 mol of silver Gelatin 2.0 g / m ² 7th layer; high-sensitivity green-sensitive silver halide emulsion layer Emulsion -II: coating amount of silver 1.4 g / m ² Sensitizing dye III: 1.5 × 10 ^-5 mol for 1 mol of silver Sensitizing dye IV: 1.0 × 10 ^-5 mol for 1 mol of silver Magenta coupler (M -1) ... 0.020 mol per 1 mol of silver Colored magenta coupler (CM-1) ... 0.002 mol per 1 mol of silver DIR compound (D-3) ... Gelatin layer containing emulsified dispersion of the yellow filter layer Yellow colloidal silver and 2,5-di -t- octylhydroquinone; 0.0010 mole gelatin 1.8 g / m ² eighth layer relative to 1 mol. Gelatin 1.5g
/ m ² 9th layer; low-sensitivity blue-sensitive silver halide emulsion layer Monodisperse emulsion (Emulsion III) consisting of AgBrI containing 0.48 μm average grain size and 6 mol% AgI ... Silver coating amount 0.9 g / m ² sensitizing dye V ... 1.3 × 10 ^-5 mol per 1 mol of silver Yellow coupler (Y-1) ... 0.29 mol per 1 mol of silver Gelatin 1.9 g / m ² 10th layer; high-sensitivity blue-sensitive emulsion layer Average particle size 0.8 μm , AgBrI containing 15 mol% of AgI Monodisperse emulsion (Emulsion IV) ... Silver coating amount 0.5 g / m ² Sensitizing dye V ... 1.0 × 10 ⁻⁵ mol per 1 mol of silver Yellow coupler (Y-1) … 0.08 mol to 1 mol of silver DIR compound (D-2)… 0.0015 mol to 1 mol of silver Gelatin 1.6 g / m ² 11th layer; 1st protective layer Silver iodobromide (AgI 1 mol% average grain) Diameter 0.07 μm) ... Silver coating amount 0.5 g / m ² UV absorber Gelatin layer containing UV-1 and UV-2. Gelatin 1.2 g / m ² 12th layer; 2nd protective layer Polymethylmethacrylate particles (average particle size 1.5 μm) 50 mg / m ² formalin scavenger (HS-1) 10 mg / m ² C ₈ F ₁₇ SO ₂ NCH ₂ CO ₂ K ... 3 mg / m ² | C ₂ H ₅ ethylmethacrylate-methylmethacrylate-methacrylic acid copolymer particles (average particle size 3.0 μm) ... 50 mg / m ² organopolysiloxane (S-1) ... 1 g / m ² Polymer hardener (HP-1) ... 2.8 × 10 ³ equivalent / 100g Gelatin layer containing gelatin. Gelatin 1.2 g / m ² back first layer; Alumina sol: 200 mg / m ² SnO ₂ sol: 50 mg / m ² Diacetyl cellulose: 600 mg / m ² Stearic acid: 200 mg / m ² Layer.

Back second layer: diacetyl cellulose… 100mg / m² Silica matting agent A (average particle size 10 μm) ... 20 mg / m² Silica matting agent B (average particle size 0.5 μm) ... 10 mg / m² Stearic acid: 100 mg / m² Fluorine-based graft polymer (Aron GF-150)… 10mg / m² Layers.

In addition to the above composition, each layer contains a gelatin hardening agent (H-
7) (excluding the 12th layer), dioctyl phthalate and surfactant were added.

The compounds contained in each layer of Sample 1 are as follows.

Sensitizing dye I; Anhydro-5,5'-dichloro-9ethyl-3,3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide Sensitizing dye II; Anhydro-9-ethyl-3,3 ' -The-
(3-Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide Sensitizing dye III; Anhydro-5,5'-diphenyl-9
-Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine hydroxide Sensitizing dye IV; Anhydro-9-ethyl-3,3'-di-
(3-Sulfopropyl) -5,6,5 ', 6'-dibenzooxacarbocyanine hydroxide Sensitizing dye V; Anhydro-3,3'-di- (3-sulfopropyl) -4,5-benzo- 5'-methoxythiacyanine C-1 CC-1 D-1 D-2 D-3 M-1 CM-1 Y-1 UV-1 UV-2 HS-1 H-7 The sample thus obtained is referred to as Sample 1-NO.1. Also,
Not only the organopolysiloxane S-1 but also various organopolysiloxanes as shown in Table 1 were used, and not only the polymer hardener HP-1 but also various polymer-containing hardeners as shown in Table 1 were used. Samples (1-NO.1 to NO.11) and comparative samples (1-NO.12 to NO.1) containing either or both of the organopolysiloxane and the polymeric hardener or a comparative hardener. 16) was produced.

Emulsion layer side surface friction coefficient was measured for these samples,
Further, put a triacetate base on the surface of the sample having a size of 5 cm × 5 cm on the emulsion layer side, and adhere the sample at 23 ° C. and 55% RH.
After standing for 1 week in an atmosphere of (relative humidity), the friction coefficient of the emulsion layer side surface was measured again except for the triacetate base.

The friction coefficient was measured according to the method of ASTM D-1814 in the United States (the sample was measured after being conditioned for 24 hours at 23 ° C. and 80% RH), and displayed as a dynamic friction coefficient with respect to the light-shielding paper for photographic film.

The transferability of the organopolysiloxane was measured as follows.

Measurement of roller contamination degree The sample is cut into a size of 5 x 5 cm and two sheets are made into one set at 23 ° C.
After conditioning the humidity in an atmosphere of 80% RH (relative humidity) for 24 hours, contact the protective layer and the back surface layer of the same sample respectively, apply a load of 80 g and store at 40 ° C and 80% RH for 4 hours. After peeling off, the transfer coefficient was evaluated by measuring the friction coefficient of the adhesive portion on the back surface. It is indicated that the smaller the value of the friction coefficient on the back surface, the larger the transfer amount of the organopolysiloxane.

Further, after exposure with white light, the following development processing was performed to measure fog and sensitivity. The sensitivity is shown as relative sensitivity with the density of (fog + 0.5) as sample 14 being 100.

The results are shown in Table 1.

Processing process (38 ℃) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixation 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dry Use in each processing step The composition of the treated liquid is as follows.

Color developer 4-Amino-3methyl-N-ethyl-N- (β-hydroxyethyl) -aniline ・ sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine ・ 1/2 sulfate 2.0g anhydrous potassium carbonate 37.5g odor Sodium iodide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water is added to make 1.

Bleaching solution Ammonium ethylenediaminetetraacetate ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Add water to adjust the pH to 1 and adjust the pH to 6.0 using ammonia water.

Fixing solution Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to make 1 and adjust to pH = 6.0 with acetic acid.

Stabilizer Formalin (37% aqueous solution) 1.5 ml Conidax (Konishi Rokusha Kogyo Co., Ltd.) 7.5 ml Add 1 to add water.

From Table 1, according to the present invention, the transferability of the organopolysiloxane is improved without impairing the photographic performance even when the outermost hydrophilic colloid layer contains the organopolysiloxane in an amount capable of obtaining a good slip property. I understand.

Example 2 X-ray photosensitive material sample 2-NO.1 was obtained by sequentially forming respective layers having the compositions shown below from the support side on both sides of a triacetyl cellulose support which was subjected to an undercoating.

Additives other than silver halide are shown in amounts per mol of silver halide unless otherwise specified.

First layer: crossover cut layer Gelatin layer containing 3 mg / m ^{2 of} dye (I).

Gelatin 0.2 g / m ² 2nd layer; emulsion layer Silver iodobromide emulsion (AgI: 1.5 mol%, average grain size 1.2 μm) ...
Silver coating amount 4g / m ² 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 1.2g Diethylene glycol 11.0g Paranitrophenyl triphenyl phosphide chloride 0.2g Gelatin 2.0g / m ² 3rd layer; protective layer sodium diethylhexyl succinate sulfonate… 0.015g / m ² glyoxal… 0.02g / m ² mucochloric acid… 0.015g / m ² polymethylmethacrylate particles… 50mg / m ² (average particle size 3 to 4 μm) Polyoxyethylene-di-nonylphenyl ether ether sodium sulfate 50 mg / m ² gelatin 1.0 g / m ² C ₈ F ₁₇ SO ₃ Na 3 mg / m ² organopolysiloxane 30 mg / m ² High Molecular hardener ... 2.5 × 10 ^-3 equivalent / 100g Gelatin dye (I) Back layer Dye (II)… 0.6g / m ² Dye (III)… 1.5g / m ² Dye (IV)… 0.75g / m ² Gelatin… 6.0g / m ² Polymethylmethacrylate matting agent… 30mg / m ² ( Average particle size 0.4μm and 3.2μm) Glyoxal… 20mg / m ² Dye (II) Dyes (III), (IV) Samples (Samples 2-NO.2 to NO.5) were prepared in the same manner as in Sample 2-NO.1 above, except that the organopolysiloxane and the polymeric hardener were changed as shown in Table 2, and the organopolysiloxane was also prepared. Comparative samples (Samples 2-NO.6 to NO.10) were prepared in which either or both of the polysiloxane and the polymeric hardener were not contained or the comparative hardener was used.

The same measurements as in Example 1 were performed on these samples.
However, the development process was as follows. The results are shown in Table 2.

Treatment process Image 30 ° C 45 seconds Settling 25 ° C 35 seconds Water wash 15 ° C 35 seconds Dry 45 ° C 20 seconds Developer Phenidon 0.4 g Methol 5 g Hydroquinone 1 g Anhydrous sodium sulfite 60 g Hydrous sodium carbonate 54 g 5-Nitroimidazole 1000 mg Bromide Add 2.5 g of potassium water to make 1000 ml and adjust the pH to 10.20.

Fixer (Part A) Ammonium thiosulfate 170 g Sodium sulfite 15 g Boric acid 6.5 g Glacial acetic acid 12 ml Sodium citrate (dihydrate) 2.5 g Add water to make 275 ml.

(Part B) Aluminum sulfate 15 g 98% sulfuric acid 2.5 g Add water to make 40 ml.

When using, add water to Part A: 275 ml, Part B: 40 ml to make 1.

From Table 2, the present invention also applies to Example 1 in the X-ray photosensitive material.
It turns out that it is as effective as.

Example 3 Layers having the compositions shown below were sequentially formed on both surfaces of a polyethylene terephthalate support which had been subjected to subbing, from the support side to obtain a light-sensitive material sample 3-NO.1 for platemaking.

Additives other than silver halide are shown in amounts per mol of silver halide unless otherwise specified.

First layer; emulsion layer Silver coating amount consisting of AgBCl containing average grain size 0.2 μm and AgBr 24 mol% 4.0 g / m ² 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.6 g Polyoxyethylene nonylphenyl ether… 50 mg / m ² Gelatin 2.5 g / m ² Second layer; Protective layer Gelatin 1.0 g / m ² Polymethylmethacrylate particles 50 mg / m ² (average particle size 3 to 4 μm) Mucochloric acid 15 mg / m ² Organopolysiloxane 0.8 g / m ² Polymeric hardener 6 × 10 ³ equivalent / 100 g Gelatin back 1st layer Dye (V) 400 g / m ² Dye (VI) 8.6g / m ² Dye (VII)… 500g / m ² Gelatin… 1g / m ² Styrene-maleic acid copolymer… 20mg / m ² 5-Nitroindazole… 8mg / m ² Cryoxal… 4mg / m ² Back No. 2 Layer Polymethylmethacrylate particles… 35 mg / m ² (average particle size 3.0.8 μm and 0.4 μm) Gelatin… 1 g / m ² Glyoxal… 20 mg / m ² Mucochloric acid: 10 mg / m ² Colloidal silica alumina: 300 mg / m ² (Ludox AM, manufactured by Du Pont) Dye (V) Dye (VI) Dye (VII) These samples were processed under the conditions shown below, and the sliding property, transfer property, sensitivity and fog were measured in the same manner as in Example 1.

Processing conditions Current image 29 ℃ 30 seconds Settlement 28 ℃ 20 seconds Water wash 20 ℃ 20 seconds Dry 45 ℃ 30 seconds Developer (stock solution) Potassium bromide 2.5g Ethylenediaminetetraacetic acid disodium 1g Potassium sulfite (55% aqueous solution) 90ml Potassium carbonate 25g Hydroquinone 10g 5-Methylbenzotriazole 100mg 5-Nitrobenzotriazole 100mg 1-Phenyl-5-mercaptotetrazole 30mg 5-Nitroimidazole 50mg 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 0.5g Diethylene glycol 60 g Sodium hydroxide Adjust the pH to 10.6 Add water to make 500 ml. (PH 10.6) When using, dilute the above stock solution with water to double volume.

Fixer (Part A) Ammonium thiosulfate 170 g Sodium sulfite 15 g Boric acid 6.5 g Glacial acetic acid 12 ml Sodium citrate (dihydrate) 2.5 g Add water to make 275 ml.

(Part B) Aluminum sulfate (18-hydrate) 15 g 98% sulfuric acid 2.5 g Add water to make 40 ml.

To prepare the liquid to be used, add about 600 ml of water to 275 ml of Part A above, then add 40 ml of Part B, and add 1 more water.
To

The measurement results are shown in Table 3.

From Table 3, it can be seen that the present invention is also effective in a silver halide photographic light-sensitive material for plate making.

〔The invention's effect〕

According to the present invention, the transferability of the organopolysiloxane is improved when the organopolysiloxane is contained in the outermost hydrophilic colloid layer of the photographic light-sensitive material in such an amount that a sufficient slipperiness can be obtained without deteriorating the photographic performance. It

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ichiro Oi 1 Sakura-cho, Hino-shi, Tokyo Konishi Roku Photo Co., Ltd. Toshiyasu Kimura Examiner (56) Reference JP-A-60-140341 (JP, A) Special Kai 52-16224 (JP, A) JP 56-66841 (JP, A) JP 57-80451 (JP, A) JP 59-31944 (JP, A)

Claims (1)

[Claims] 1. A photographic light-sensitive material having at least one hydrophilic colloid layer on the outermost surface on a support, wherein at least one hydrophilic colloid layer on the outermost surface contains an organopolysiloxane and reacts with gelatin. Having at least two dura mater in the same molecule for molecular weight 3000
A photographic light-sensitive material characterized by being hardened by a polymeric hardener which is the above compound.