JPS62269139A - Photographic sensitive material improved in transferability of organopolysiloxane - Google Patents

Abstract

PURPOSE:To prevent transfer even in the case of adding a large amount of polyorganosiloxane and trouble in conveyance by hardening the uppermost hydrophilic colloid layer containing organopolysiloxane with a polymer hardener. CONSTITUTION:At least one of the uppermost hydrophilic colloid layers contains organopolysiloxane and it is hardened with the polymer hardener. The organopolysiloxane to be used is not especially limited in viscosity, but it is proper to control its viscosity generally to 20-100,000cSt measured at 25 deg.C, and to regulate its molecular eight to 1,000-1,000,000, and it is preferred to add it in an amount of 0.3-30wt% of the colloid of the uppermost hydrophilic colloid layer. the polymer hardener is a compound having a number average molecular weight of >=3,000 and at least 2 hardening groups for reacting with gelatin in the same molecule, and especially preferable ones are polymers having active vinyl groups or their precursor groups combined through long spacers with the main chain of the polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photographic material containing organopolysiloxane, and more particularly to a silver halide photographic material containing stably organopolysiloxane.

[Background of the invention]

A silver halide photographic light-sensitive material consists of a support such as paper, glass, cellulose acetate film, or polyester film, and at least one photosensitive layer coated on the support. Usually hydrophilic colloids, especially gelatin, are used.

This coated film using gelatin as a binder has a high coefficient of friction against other metal surfaces or gelatin surfaces.For this reason, photographic materials that use hydrophilic colloids, especially gelatin, as a binder are generally Silver halide, which is used as a photosensitive material, is sensitive to pressure, so it is easily scratched.
Scratches caused by friction or the like sometimes cause pressure fogging, desensitization due to pressure, etc., and have a fatal effect on photographic images.

For this reason, in silver halide photographic 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 improve the film surface. Measures have been taken to roughen the surface and reduce the contact area to control the friction coefficient, prevent fogging caused by pressure, or protect the photographic material 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 been disclosed, for example, in U.S. Pat.
It is known from the description in No. 7.

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 if they are used in large quantities, the transparency of the photosensitive material decreases, resulting in a deterioration of the sharpness of the image. ing.

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 adhere to each other.

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

Furthermore, solid paraffin has poor dispersibility, and in particular, dispersibility strongly depends on temperature, making it difficult to create a stable and uniform dispersion of fine particles, and solid paraffin tends to adhere to the walls of containers, pipes, etc. There are drawbacks such as the need to keep the entire container or pipe warm to eliminate this.

Furthermore, a method of controlling the slipperiness of photosensitive materials using a surfactant is also known, but the surfactant dissolves into the processing solution during processing, resulting in problems such as foaming of the processing solution. There are disadvantages such as the amount of use is limited because of this.

In particular, when fluorine-containing surfactants are eluted into the processing liquid, they tend to stick as dry deposits on the conveyor rollers in the processing machine.
This roller contamination causes problems such as uneven development.

Also known is a method in which a photographic emulsion layer, protective layer or back layer contains a liquid organopolysiloxane to make the surface of the photosensitive material slippery. For example, U.S. Pat.
No. 42,522, using dimethyl silicone in combination with certain surfactants, and using a mixture of dimethyl silicone and diphenyl silicone, as described in U.S. Pat. No. 3,080,317. methods using triphenyl-terminated medylphenyl silicones as described in British Patent No. 1,143.118; A method using alkyl silicone and a specific surfactant, a method using a polysiloxane having a long-chain alkyl group in the side chain as described in Japanese Patent Publication No. 53-292, and a method described in Japanese Patent Publication No. 55-92843. A method using a polysiloxane having a polyoxyethylene group in the side chain as described in JP-A-49-125015, a method using a silicone polymer and a cationic fluorosurfactant as described in JP-A-49-125015; Showa 60-1403
No. 41, JP-A-60-140342 and JP-A-60
A method using a polysiloxane having a special functional group as described in No. 140343 is known.

Although these compounds improve the slip properties of photosensitive materials, they must be contained in large amounts in order to obtain sufficient slip properties. However, if a large amount is used, the organopolysiloxane will be transferred to other objects when it comes into contact with it, and if this occurs during the manufacturing process, there is a problem in that it will cause transportation failures and produce defective products.

As a result of intensive research to solve this problem, the inventors of the present invention found that increasing the hardness of the organopolysiloxane-containing layer reduces the above-mentioned transfer, and that if the hardness of the silver halide emulsion layer increases to the same extent. The present invention was achieved by discovering that the sensitivity could be degraded.

[Purpose of the invention]

The purpose of the present invention is, firstly, to provide a silver halide photographic material that does not cause transfer and transport failure even when a large amount of polyorganosiloxane is added; It is an object of the present invention to provide a silver halide photographic material that does not cause transfer even when added and does not affect photographic performance.

[Structure of the 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, at least one of the hydrophilic colloid layers on the outermost surface containing an organopolysiloxane and a polymer. This is achieved by a photographic material characterized by being hardened with a hardening agent.

The present invention will be explained in detail below.

Organopolysiloxanes used in the present invention include U.S. Pat.
, 694,637, Japanese Patent Publication No. 39-15714, British Patent No. 1,030,811, British Patent No. 1,143,118,
1,528,656, 1,275,657, 1,278,402, 1,313,384, Special Publication No. 51-15740, Special Publication No. 45-34230, No. 46-27428 JP-A-49-62128, JP-A-49-62127, JP-A-53-292, JP-A-55-49294, JP-A-60-140341, JP-A-60-140342, JP-A-60-140343 , same 6
No. 0-188945, No. 80-231704, No. 60
-231720, 60-240781, 60-
No. 243167, No. 60-240732, No. 60-2
No. 45638, No. 61-216, No. 61-232,
Compounds described in JP-A No. 61-260 and the like are included.

Among these organopolysiloxanes, preferred are those having a structural unit represented by the following general formula (1).

General formula (1) %Formula% Here, R3 represents a hydrogen atom, a hydroxyl group, or an organic group, and R3 represents an organic group.

Examples of organic groups for R1 and R3 include alkyl groups (preferably those having 1 to 18 carbon atoms), substituted alkyl groups (e.g., carboxyalkyl, aminoalkyl, alkylaminoalkyl, mercaptoalkyl, alkoxyalkyl, glycidyloxyalkyl, aralkyl, aryl). loxyalkyl, -R, -R, -R5 (Ri is alkylene group, R
4 is a group in which two or more oxyalkylene groups are connected, R5
represents an alkyl group. ), alkenyl groups (eg, vinyl, allyl, etc.), alkoxy groups (eg, methoxy, ethoxy, etc.), aromatic groups (eg, phenyl), and groups containing these groups.

In addition, the terminal of the organopolysiloxane has the following general formula [
(2) Preferably, those having a structural unit represented by [2]] are preferred.

General formula (II) R, -5i-0- R.

Here, Ro, R9 and R8 each represent a hydrogen atom, a hydroxyl group or an organic group, and this organic group is R
Examples of organic groups for R3 and R3 include those listed above.

There are no particular limitations on the viscosity of the organopolysiloxane used in the present invention, but those exhibiting a viscosity in the range of 20 to 100,000 centistokes when measured at 25°C are suitable.

Furthermore, the molecular weight of the polysiloxane according to the present invention is 1000.
A range of 1,000,000 to 1,000,000 is appropriate and can be used depending on the purpose, but preferably 2,000 to 5ooo.

is within the range of

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

C11゜ CI+2-4: QC, H, 10CH, n=7S -5 〇 C, He(n) mine C.I.

"0-CH, -CIl-CH2 ゝ\/' CHi3-St-CHi ■ CHi -ta ShiH, L, 113 Rishi 113 1.rl'+3Nl+2 CH2 NIICII, C11 2NH.

S -21 S-22 R Ht 0 (CHICI20hCH2CH!SO, CH=CHt
-3O to 113 and I13 ulhS-
36 S-37 Q+m+n=1O~12 &+s+n=12~15 The organopolysiloxane used in the present invention has a ratio of 0.3 to 30 relative to the hydrophilic colloid in the outermost hydrophilic colloid layer.
It is preferable to contain it in a range of % by weight.

The polymeric hardener in the present invention means a compound having a molecular weight (number average molecule ff1) of 3,000 or more and having at least two hardening groups in the same molecule to react with gelatin.

Here, the dura mater group for reacting with gelatin etc. is
Examples include aldehyde groups, epoxy groups, active halide groups (such as dichlorotriazine), active vinyl groups, and active ester groups.

The number of these groups in the polymer hardener is preferably at least 2, but preferably 10 to 500011J.

Further, as for the molecular weight, those having a molecular weight of about 3,000 to 500,000 are preferably used.

Generally, a hydrophilic polymer moiety having a hardening group for reacting with gelatin is preferably used, but even if it is not hydrophilic, a hydrophilic colloid (e.g. gelatin) can be used.
It can also be used by emulsifying and dispersing (dissolving and dispersing in an organic solvent if necessary).

Examples of the polymeric hardening agent used in the present invention include dialdehyde starch, polyacrolein, and U.S. Pat. No. 3,396
Polymers having aldehyde groups such as the acrolein copolymers described in US Pat. No. 3,623,87
Polymer having epoxy groups as described in No. 8, U.S. Patent No. 3
, No. 382, 827, Research Disclosure Magazine 17333 (1978), etc. Polymers having dichlorotriazinyl groups, JP-A-56-668
Polymers having active ester groups described in No. 41, JP-A-56-142524, U.S. Pat. No. 4,16
No. 1,407, JP-A-54-65033, Research
Examples include polymers having an active vinyl group or a group serving as a precursor thereof, as described in Disclosure Magazine 16725 (1978), etc. Polymers having an active vinyl group or a group serving as a precursor thereof are preferred, and among them, particularly Particularly preferred are polymers in which an active vinyl group, or a group serving as a precursor thereof, is bonded to the polymer main chain by a long spacer, as described in Japanese Patent Publication No. 142,524/1983.

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

P-1 NtlL;(niHs, hUHtsυ3ea
OCH*CHtOCOCH*CHtSOtCH=C
HtII P-2 C11゜Summer-IF'-3 P-4 I P-5 P-6 P-7 P-8 P-9 NHl
Ht to NHH to NHCO 11tSυ2CIl=CH*
IP-10 0H HP-11 CI+3 CI+3 HP-12 υ II P-13 HP-14 HP-15 HP-18 CH3 NIIC(CH3) tcHtsO3Na OiCHtSoupNHCONHCOCH*CHtC(!P-17 Ntlt NHIC ;HkeT , CH0H1'-f8 : NIICIICO tool) (P -19 -Co - (C11? Homabe0NII(C1ty)y N
SakiOHt)y Nll Tollt HP-20 Ki113 HP-21 HP-22 HP-23 (CH2 piece C0OH HP-24 HP-25 Nut 011 0-CJ, 5OtCH=CH.

IP-26 HP-27 1-IP-28 The polymer hardener of the present invention may also contain at least two hardening groups in the same molecule from the beginning to react with gelatin, like the polymers mentioned above. Polymers with more than one hardening group can be used, but they can be coated using a gelatin hardener and a polymer that reacts with it to give a polymer with at least two hardening groups in the same molecule. It is possible to create a polymeric hardener in the hydrophilic colloid layer, thereby achieving the object of the present invention.

Thus, as hardeners for gelatin used to make polymeric hardeners in hydrophilic colloid layers, small molecule hardeners such as rTheTheo by T.H.
ry to the Photographic Pr
The low-molecular hardening agents described in pages 77 to 84 of the 4th edition are used, and among them, low-molecular hardening agents having a vinyl sulfone group or a triazine ring are preferred.
In particular, JP-A-53-41221 and JP-A-60-2251
The hardeners described in No. 43 are preferred.

Specific examples of gelatin hardeners that provide polymeric hardeners according to the present invention are shown below.

H-1 (C111=CH3O2CII2CONHCH)
2H-2(CH2=CHSO, CH1CONlIC11
2), -C)l.

fl-3C11,=Cll5O,CI+2C11CI1
．． SO, CII=CI+.

O12 tl-4CI+,=CH-C1l-5o2-CH=CI
I.

H5CIL=CII 5OtC1ltOCIIt
Sot CH=CIltLl 6 CHt=
CIISOtCHtCHtCIItSOtCII=CH
tH8011C(C1lt)y CHO H-9 formalin H-14CH,=CH3OtCH2CH,SO,C)l
=cH.

H-15 (CIIt=CHSO, CH2 juice CH-16 (
(CHt=CH3OICI2cattyC)・l(,NCR,C
1.Salt for SO, In addition, as a polymer used to make a polymer hardener in the existing aqueous colloid layer, at least two nucleophilic groups in the same molecule that react with the Iin agent of gelatin are used. For example, British Patent No. 2,0
A polymer having a primary amino group described in No. 11,912,
Polymer having sulfinic acid group described in Special No. 13F1 No. 56-4141, U.S. Pat. No. 4,207゜1
Examples thereof include a polymer having a phenolic hydroxyl group as described in US Pat.

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

-3Q-4 Published by CH, -C11) llz Ht The method for synthesizing the polymer hardener used in the present invention is shown below.

Synthesis Example I Synthesis of N-(3-(chloroethylsulfonyl)propioyl)aminomethylacrylamide In the reaction vessel of 2Q, distilled water 1400o + 12, and sodium arsenite 224g
, sodium bicarbonate 2209 was 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 the dropping was completed, 49% sulfuric acid 1609 was added, and the precipitated crystals were filtered.
It was further washed with 400 ml of distilled water. Add this filtrate and washing liquid to a 3Q reaction vessel, and add 2469 methylene bisacrylamide to 480 m12 of distilled water and 14 m2 of methylene bisacrylamide.
A solution dissolved in 80 ml of ethanol was added dropwise at 5° C. over about 30 minutes. After the reaction sample was left in the refrigerator for 5 days to complete the reaction, the precipitated crystals were collected by filtration, washed with 800 ml of cooled distilled water, and then washed with 2000 ml of distilled water.
Recrystallize from a 50% ethanol aqueous solution of 12 to obtain 21
A white powder of No. 09 was obtained. The yield was 49% and the m.p. p. The temperature was 192°C or higher (decomposition).

Synthesis Example 2 Synthesis of N-(2-(chloroethylsulfonyl)acetyl)aminomethylacrylamide Add methanol to the reaction solution of tC. 2(ln12, N-
Methyloacrylamide 8G. 09 was added thereto, and 40 ml of concentrated hydrochloric acid was added at room temperature while stirring. After stirring for 16 hours, 0.49 of hydroquinone monomethyl ether was added, and methanol was distilled off using an evaporator. To the remaining oil of 62 and 49, add 1009% of chloroethanesulfonylacetamide and 0.0% of hydroquinone monomethyl ether.
329, I) - Add 0.229 of toluenesulfonic acid,
Heating to 150°C produces C I, O! + was distilled off.

The reaction was completed in about 15 minutes, and the remaining crystals were recrystallized from 250 m of 50% ethanol aqueous solution to give 611? A white powder was obtained. The yield was 42%.

Synthesis Example 3 Poly-N-(3-(vinylsulfonyl)propioyl)
Aminomethylacrylamide co-acrylamide 2
- Sodium methylpropanesulfonate (HP-3) 5.6 ml of the monomer of Synthesis Example 1 was added to 200 ml of the reaction solution.
59. Sodium acrylamide-2-methylpropanesulfonate9. Add 80++ l of 50% ethanol aqueous solution, stir to dissolve, and add 80++ liters of 50% ethanol aqueous solution, stir to dissolve, and add 80++ liters of 50% ethanol aqueous solution.
The temperature was raised to 0°C, and 0.19 of 2.2'-azobis(2,
4-dimethylvaleronitrile) was added, and after another 30 minutes, the same amount of the same was added, and heating and stirring were continued for 1 hour.

After that, it was cooled to 10℃ and a mixture of 2.59 triethylamine and 80mf2 ethanol was added.
Stirring was continued for 3 hours, the reaction sample was added to 11 acetone, the precipitate formed was collected by filtration, and dried under vacuum for 12.4 hours.
A white polymer of FI was obtained. The yield was 8596, the intrinsic viscosity [η] of this polymer was 0.227, and the vinyl sulfone mixture was 0.95×10′.

Mn=7200 Synthesis ('A 4 Poly-N~(2-(vinylsulfonyl)acetyl)aminomethylacrylamide-coacrylamide
(IP-7) Add 53.7 g of the monomer of Synthesis Example 2, 163.3 fI of acrylamide, and 1955° of methanol to a 3000 m II reaction vessel.
Stir to dissolve, heat to 60°C while passing nitrogen gas, add 6.2g of 2.2'-azobis (2,4-dimethylvaleronitrile), and heat for 4 hours, then heat to room temperature. 20.2° of triethylamine was added, stirred for 2 hours, and the precipitate was collected by filtration and dried under vacuum.
4.3 g of white polymer was obtained. The yield was 92.7%,
The vinyl sulfone content of this polymer is 0.50X10
'equivalent/2 polymers. Hn=4900 Synthesis Example 5 Potassium polyvinylbenzenesulfinate-co-acrylamide-2-methylpropanesulfonic acid sodium
(Q-1) Add 45.89 ml of sodium acrylamide-2-methylpropanesulfonate, 20.69 ml of potassium vinylbenzenesulfinate, 180 ml of ethanol, and 12° distilled water to a 500n+I2 reaction container, and heat to 75°C while stirring. , (2,2'-
Azobis-(2-amine)propane) dihydrochloride 0.82
Add 9 and heat for 4 hours, then let it cool to room temperature.
Ethanol 72111I2 and distilled water 278ml were added and filtered to obtain a colorless and transparent viscous liquid.

The viscosity of this polymer solution at 25°C is 3.25 cp
.

The solid content concentration is 1O, 3WT%, and the sulfinic acid content is 6.
2X to-” equivalency/9 and ivy. rh=1
6,000 and other polymeric hardeners can be easily synthesized based on these synthesis examples or the methods described in the above-mentioned patent specifications. Some compounds are also commercially available.

When using the polymeric hardener of the present invention, the amount used can be arbitrarily selected depending on the purpose.6 Usually, 1m groups that react with gelatin are added to 100g of dry soot gelatin. Polymeric hardeners ranging from 5.times.10@-2 to 5.times.10@-2 equivalents are used. Particularly preferred is a range from 0.5X'IO'')5 to 2X10-2I.

As the hardening agent for the outermost hydrophilic colloid layer (hereinafter referred to as the eel surface layer of the present invention) containing the organopolysiloxane according to the present invention and hardened with a polymer hardener, the above-mentioned hardeners may be used. High polymer hardness 11! In addition to using punishment in China and Germany, Japanese Patent Publication Nos. 51-78788, 5341221, and 1jO
-225143, U.S. Patent No. 3,325,287
No., Same No.: (.

No. 945.853, JP-A-59-31944, JP-A No. 55
Ike's low molecular weight hardening agent (Fr?+ <
3000> can be used together, and in the present invention, it is preferable to use them together.

Hardening agents that can be used in combination include compounds having a reactive halogen atom such as 2-human Roxy 4,6-dichloro-1,3,5-1-riazine, and reactive hardeners such as divinyl sulfone. Compounds with olefins, isocyanates, aziridine compounds, 4 epoxy compounds, mucochloric acid, chrome light bread, aldehydes, ■-
Specifically, the compounds shown in [1-1] to H-21 can be obtained by -i&:.

The outermost layer of the present invention is a transfer layer of organopolysiloxane.
rl+ 7-rutme, 15j moisture power 1, 0~5
, Olt:'il::1.5-:), preferably in the range of 0; on the other hand, if the photographic light-sensitive layer is a silver halide emulsion layer, the hardening is preferably in the range of 1.5-10, from the viewpoint of desensitization. Especially 2~
It is preferable to harden in the range of 7. Here, the degree of swelling is a value measured as follows.

Measurement of degree of swelling: A sample is immersed in a developer at 38° C. and swelled for 30 seconds, which is expressed by X in the following formula.

X = (Film thickness increased due to swelling) / (Film thickness when dry) The outermost layer of the present invention has 3 organopolysiloxanes, and is hardened with a polymeric hardening agent, and is otherwise halogenated. It can take a structure known as a protective layer for silver photophobic materials. The height of the outermost surface Jt, 4 is 0.1 to 5.
A range of 0 to III+ is appropriate, preferably 0.3 to
The range is 1.5 μm.

In order to have the organosiloxane used in the present invention in the outermost layer of the present invention and harden it with a polymer hardener, there are two methods: adding both to the coating solution in advance, and a method of adding the polymer hardener or A polymer that provides a polymeric hardening agent is added to the outermost layer, and an organopolysiloxane or an organopolysiloxane and a hardening agent that reacts with the polymer to form a polymeric hardening agent are added to the outermost layer. Alternatively, there is a method of infiltration, but it is preferable to add both to the coating solution in advance from the viewpoint of the GI-forming cococost effect.

Methods for adding the two to the coating solution include dispersing both in a hydrophilic colloid solution, such as a gelatin solution, in the presence of a dispersant, and then adding them to the desired coating solution, or adding both to the coating solution as they are. There are methods such as dispersion and coating.

As the dispersant for organosiloxane, surfactants commonly used for photography can be used, such as anionic surfactants, nonionic surfactants, amphoteric surfactants, or cationic surfactants as appropriate. Dispersion can be carried out using an ultrasonic homogenizer or a valve homogenizer, depending on what is selected. The preferred particle size is in the range of 0.005 to IO .mu.m; if the particle size is too small beyond this range, the effects of the present invention, especially the slipperiness, will deteriorate, and if it is too large, devitrification will occur, making it undesirable as a photosensitive 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 layer of the photographic light-sensitive material of the present invention. , agar, gum arabic, alginic acid, e.g. acetyl content 19-26
cellulose derivatives such as cellulose acetate hydrolyzed to %, acrylamide, imidized polyacrylamide, casein, vinyl alcohol polymers containing urethane carboxylic acid groups or ananoacetyl groups such as vinyl alcohol, vinylanoacetate copolymer, polyvinyl alcohol , polyvinylpyrrolidone,
Hydrolyzed polyvinyl acetate, a polymer obtained by polymerizing a protein or a saturated unyanlated protein with a monomer having a vinyl group, etc. can be used.

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

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

These gelatin hardening agents are described, for example, in U.S. Pat.
No. 9,644, No. 3.642.486, No. 2.7
No. 26,162, No. 2.816,125, No. 3,
No. 047,394, West German Patent No. J, No. 085,663, British Patent No. 1,033,518, Special Publication No. 4G-35
49, PB Report No. 19921, U.S. Patent No. 2950,197, U.S. Patent No. 2,964,404, U.S. Patent No. 2
, 983.611, 3,271.175, 2,938,892, 3,640°720, 3,058,827, 2,994.811 ,
British Patent No. 822,061, British Patent No. 1,042,083
No. 1,202,052, No. 1,230,35
No. 4, West German Patent No. 872,153, Special Publication No. 1972-2
No. 9622, No. 47-25373, Special Publication No. 47-87
No. 36, JP 46-38715, JP 49-73
No. 122, JP-A-48-74832, JP-A-49-2
No. 4435, JP-A-48-43319, JP-A-48-
No. 43320, Japanese Patent Application Publication No. 49-116154, Patent Application No. 116154
It is described in Japanese Patent Application No. 8-112325, Japanese Patent Application No. 110996-1982, Japanese Patent Application No. 15096-1987, etc.

The amount of hardening agent 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, but the amount of hardening agent may be within any range that does not impair the effects of the present invention. It is desirable that the content in the dry state is 0.01% by weight or more, preferably 1% by weight or more.

The hydrophilic colloid layer of the photographic light-sensitive material of the present invention may optionally contain photographic additives other than the hardener, such as gelatin plasticizers, surfactants, ultraviolet absorbers, antistain agents, PHFI moderators, Antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, development speed regulators, matting agents, etc. can be used within the 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. No. 2,960. J04, Japanese Patent Publication No. 43-4939, West German Patent No. 1,904,604, Japanese Patent Publication No. 48-63
715, Japanese Patent Publication No. 45-15462, Belgian Patent No. 782,833, U.S. Pat. copolymer,
As ultraviolet absorbers such as dextran sulfate,
For example, Special Publication No. 4g-736, Special Publication No. 4g-5496, Special Publication No. 41572, Special Publication No. 48-41572, Special Publication No. 4g-30492.
No. 1255, U.S. Patent No. 3,25
3,921, British Patent No. 1.309.349, in particular 2-(2'-hydroxy-5'
-tert-butylphenyl)benzotriazole,
2-(2'-hydroquine-3',5'-tert-
butylphenyl)benzotriazole, 2-(2'-hydroquine-3'-tert-butyl-5'-butylphenyl)-5-chlorohencytriazole, 2-(2'
-Hydroxy-3', 5'-di-tert-butylphenyl)-5-chlorobenzenetriazole, etc., as surfactants include British Patent No. 548.532, British Patent No. 1,216,389, and U.S. Patent No. 3.026. .202
No., U.S. Patent No. 3,514,293, Special Publication No. 1977-2
6580, Special Publication No. 17922, Special Publication No. 17922, Special Publication No. 17922-
No. 17926, Special Publication No. 13166, Special Publication No. 1977
-20785, French Patent No. 202.585, Belgian Patent No. 773.459, etc., in particular radium-di-2-ethylhexylsulfosuccinate, sodium moamyl-decylsulfosuccinate, Examples of anti-staining agents such as sodium dodenlebenzenesulfonate and sodium triisopropylnaphthalenesulfonate include U.S. Pat. No. 2,360,210, U.S. Pat. '300
No. 3,700.453, etc., especially 2-methyl-5-hexadecyl-hydroquinone,
Examples of antistatic agents such as 2-methyl-5-seC-octadecyl-hydroquinone and 2,5-tert-octylhydroquinone are disclosed in Japanese Patent Publication No. 46-24159 and Japanese Patent Publication No. 4i! l-89979, U.S. Patent No. 2.81112
．． No. 157, No. 2,972.535, Japanese Unexamined Patent Publication No. 1972-
2 (No. 1785, JP-A No. 48-43130, JP-A No. 4
L90391, Special Publication No. 39312, Special Publication No. 46-39312, Special Publication No. 46-39312
No. 8-43809, Special Publication No. 49-4853, Special Publication No. 4
9-64, Japanese Patent Publication No. 47-8742, Japanese Patent Publication No. 47-3
Compounds described in U.S. Pat. No. 3,627, etc., and as matting agents, compounds described in U.S. Pat. In particular, mention may be made of silica gel having a particle size of 0.5 to 20 μm, and polymers of polymethyl methacrylate having a particle size of 0.5 to 20 μm.

Supports used in the photographic material of the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass temporary, cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, and polypropylene films. Typical examples include polycarbonate film, polystyrene film, etc.
These supports are appropriately selected depending on the intended use of the photosensitive material.

The present invention is applicable to various halogen-arsenic photographic materials having hydrophilicity = 11 phytolayers, such as general negative photosensitive materials↑
1. General reversal photosensitive material, general positive photosensitive material 1'1
It can be applied to direct positive photosensitive materials, special purpose (for example, printing, X-ray, high resolution, infrared, ultraviolet, etc.) halogen arsenic photographic materials, and the like.

〔Example〕

Specific embodiments of the present invention will be described below, but it is important to understand how the present invention can be carried out. The types are not limited to these.

In all the examples below, the amount added in the silver halide photographic material f') is per 112 unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver.

Example 1 Multilayer color photophobic material sample 1-No. 1 was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side.

1st layer; antihalation layer Black = gelatin glue that holds 10 id silver.

Gelatin 2.2 FI/m2 Second layer; Intermediate layer 2. Gelatin layer containing an emulsified dispersion of 5-di-t-octylhydroquinone.

Cera+: / 1.21F/m2 Third layer; low sensitivity red-sensitive silver halide emulsion layer average grain size 0.
30μ..., 8g! Monodisperse emulsion consisting of eight girls containing 6.0 mol% (emulsion I)...silver coating amount 1.8 g/+s"
Sensitizing dye 1... 6 x 10' moles per mole of silver Sensitizing dye ■... 1.0 x 105 moles per mole of silver Cyan coupler (C-1)... 0 per mole of silver .06 mol colored cyan coupler (CC-1>... 0.003 mol DIR compound (D-1) per 1 mol silver... Q, (1015 mol DIR compound (D-1) per 1 mol silver) 2)... 0.002 mol gelatin per 1 mol silver 14 g/rn'' 4th layer: High sensitivity red-sensitive silver halide emulsion layer Average grain size 0.
Monodisperse emulsion (emulsion ■) consisting of AgBr1 containing 5 μra, Agl 7.0 mol %...Silver coating amount 1.3 g/m" Sensitizing dye I... 3 x 10-' mol for 11 mol Sensitizing dye...
- t, ox to-' Morcyan coupler (C-1) for 1 mol of silver... 0.02 mol for 1 mol of silver Colored cyan coupler (CC-1)... for 1 mol of silver 0.0015 mol DIR compound (D-2)... O, oot mol gelatin 1.0/m'' per 1 mol of silver 5th layer: Same as the intermediate layer 2nd layer, gelatin layer.

Gelatin 1.0g/+u' No. 68: Low-sensitivity green-sensitive silver halide emulsion layer Emulsion-I
...Amount of coated silver 1.5g/m'' sensitizing dye■... 2.5X 1G-'mol sensitizing dye■ for 1 mole of silver・
... 1.2X tG-' mol magenta coupler (M-1) for 1 mol of silver... 0.050 mol for 111 mol Colored magenta coupler (CM-1)... for 1 mol of silver and 0.009 mol D[rL Compound (D-1)... o, ooto mol Dlr per 1 mol of silver! Compound (D-3)... 0.003Q mol gelatin per 1 mol of silver 2.0 g/+a' 7th layer; Highly sensitive green-sensitive silver halide emulsion layer Emulsion - ■
...Coated silver amount: 1.4 g/m'' sensitizing dye ■... 1.5X 10-' mol sensitizing dye ■ per 1 mole of silver
... 1 mole of silver. OX 10-' mol Magenta coupler (M-t)... 0.020 mol per mol of silver Colored magenta coupler (CM-1)... 0.002 mol DIR compound (D -3)... 0.001Q mol gelatin 1.89/+++ per mol of silver 8th layer: yellow filter layer containing an emulsified dispersion of yellow colloidal silver and 2.5-di-t-octylhydroquinone. Gelatin layer containing. Gelatin 1
．． 59/TI+'' 9th layer: Low sensitivity blue-sensitive silver halide emulsion layer Monodispersed emulsion (emulsion ■) consisting of AgBr I with an average grain size of 0.48 μm and containing 6 mol% of Agl... Silver coating amount 0.9 g /m" Sensitizing dye ■... 1.3X 10-' mole per mole of silver Yellow coupler (Y-1)... 0.29 mole per mole of silver Gelatin 1.9 g/m' 1st O layer: high sensitivity blue sensitive emulsion layer average grain size 0.8 μm, Ag containing 15 mol% Agl
Monodispersed emulsion (emulsion ■) consisting of Br1...Silver coating amount 0.5 g/m'' Sensitizing dye■...1.OX to 'mol yellow coupler (Y-1) per 1 mole of silver ... 0.08 mol to 1 mol of silver DIR compound (D-2)... 0.0015 mol to 1 mol of silver Gelatin 1.6 g/m2 11th layer; 1st protective layer Silver iodobromide (Agl 1 mol% average particle size 0107 μm)・
... Silver coating amount: 0.5 g/m' Gelatin layer containing ultraviolet absorbers UV-1 and UV-2. Gelatin 1.21F/i' 12th layer; 2nd protective layer polymethyl methacrylate particles (average particle size 1.5 μm)...50 ng/So2 formalin scavenger (IIS-1>...10 mg/m2
Ethyl methacrylate-methyl methacrylate-1-methacrylic acid copolymer particles (average particle size 3.0 μm)...50
+ag/n+2 Organopolysiloxane (S-1)...1g/I
I2 polymer hardener (IIP-1>...2.8x
Gelatin layer containing 10 equivalents of gelatin. Gelatin 1.2g/a” back 1st layer; Alumina sol -2001111
F/Ill"SnO,
・-5011g/II' diacetylcellulose
...600mg/...2 stearic acid
...A layer consisting of 200B/-2.

Hack second layer; diacetylcellulose...rootag
/m2 Silica matting agent A (average particle size 10) t m) −
20+B, 'm' silica matting agent B (average particle size 0.5μ
+a)・-10B/m2 stearic acid
...100+nfI/m2 Fluorine-based graft polymer (Alotoflux GF-150)...110l11/m
A layer consisting of 2.

In addition to the above composition, each layer contains a gelatin hardener (+1-
7> (except for 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-9-ethyl-3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide sensitizing dye ■; anhydro-9-ethyl-3,3'-di (3-sulfopropyl)-4,5.

4',5'-diben'zothiacarpocyanine hydroxide enhancing dye ■; anhydro-5,5'-diphenyl-phob[l-pyl)oxacarboxylic acid dye ■, anhydro-9-ethyl-3 ,3'-no(3-sulfob[lpil)-5,6,5'.

6'-dibenzooxalupocyanine hydroquine sensitizing dye ■; anhydro-3,3'-di(3-sulfob[1 pyru)-4,5-benzo-5'-methoxythiacyanine ll I1 CO.

C& C,ll9(t) v 2 (:, 11゜ The sample thus obtained is designated as sample 1-NO,I.

In addition, as shown in Table 1, various types of organoborin [J-xane] are used, including not only organoborin [J
Moreover, in addition to the 6-molecule hardener II P-1, we also tested samples using various gold polymer hardeners as shown in Table 1 (I
No, 1-No, II) and comparative samples containing either or both organoborin xane and polymeric hardener (No, 1-No, II) and comparative samples containing either or both organoborin
No. 0.12 to No. 16) were prepared.

What about the emulsion layer side surface of these samples? The L coefficient was measured, and a triacetate base was placed on top of the emulsion layer side of a sample with a size of 5 cm x 5 am, and the sample was placed in close contact with the sample.
After being left in an atmosphere of 23 DEG C. and 155% RH (relative humidity) for one week, the friction coefficient of the surface of the emulsion layer was measured again, excluding the triacetate base.

The coefficient of friction was measured according to the method of ASTM D-1814 in the United States, and the sample was humidified at 23° C. and 80% RH for 24 hours. ), expressed as the coefficient of kinetic friction against light-shielding paper for photographic film.

Further, the transferability of the organopolysiloxane was measured as follows.

Measurement of Roller Contamination Degree Samples were cut into pieces of 5 x 5 cm and two pieces were made into a set, and the protective layer of each sample was moistened in an atmosphere of 23°C and 80% RH (relative humidity) for 24 hours. A load of 809 was applied to the sample and the back layer was applied, and the sample was stored for 4 hours at 40'C and 80% RH.The load was then removed, the sample was peeled off, and the friction coefficient of the adhesive portion on the back side was measured to evaluate transferability.

The smaller the value of the back surface friction coefficient, the larger the amount of organopolysiloxane transferred.

Further, after exposure to white light, the following development treatment was performed, and fog and sensitivity were determined by Ji. The sensitivity is (fogging +0.5
) is expressed as a relative sensitivity with sample 14 set as 100.

The above results are shown in Table 1.

Processing process (38℃) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water
Wash 3 minutes 15 seconds Fix
Wash with water for 6 minutes and 30 seconds Stabilize for 3 minutes and 15 seconds
Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

Color Development 1 Gas and Liquid 4-Amino-3methyl-N-ethyl-N-(β-hydroxyethyl)-aniline, sulfate 4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine, 1/2 sulfate 2.09 Free+potassium carbonate 37.5g (chicken 1-lium 1.3g2l, lilo-I-liacetic acid, 3sl-lium salt (monohydrate)
2.5g potassium hydroxide 1.0
g Add water to make 11.

White residue Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid
Add 10.0ml water to 11
Then, adjust the pH to 6.0 using aqueous ammonia.

Fixer ammonium thiosulfate 175.0y Anhydrous thorium sulfite 8.5g Sodium metasulfite 2.32 years! 11 and adjust the pH to 6.0 using monoacetic acid.

Stable liquid formalin (37% aqueous solution) 1.5m
& Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5m
Add l water to make 11.

From Table 1, according to the present invention, the outermost hydrophilic colloid layer has 1'! It can be seen that the transferability of the organopolysiloxane is improved without impairing the photographic performance by including three pieces of organopolysiloxane in an amount that provides good slip properties.

Example 2 Each layer having the composition shown below was sequentially formed on both sides of an undercoated i-lyacetyl cellulose support from the support side to obtain X-ray photosensitive material sample 2-No.

I got 1.

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

1st layer; Crossover cut layer Gelatin layer containing 3I1g/112 of dye (]).

Gelatin 0.2g/Ku2 2nd layer; Emulsion layer Silver iodobromide emulsion (gelatin: 1.5 mol%, average grain size 1.2
μm) - Silver coating m 4y/la”4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene
...162g diethylene glycol
...11.0g Halanitrophenyltriphenylphosphite chloride ...0.29 Gelatin ...2.0g/m'' Third layer: Protective layer Sodium diethylhexyl succinate sulfonate
=・0.0159/m2 Glyoxal...0.029/m" Mucochloric acid...0.0159/m' Polymethyl methacrylate particles...50+H/m' (
Average particle size: 3-4μm) Sodium polyoxyethylene-di-nonylphenyl ether sulfate...50B/m'' gelatin
...1.09/m'CaFl?
SO3Na -3mg/m"Organopolysiloxane...30m9/m'
Polymer hardener...2.5x 10-3 equivalentffl/
1oo9 gelatin dye (1) Back layer dye (II) ...0.6
9/m” dye (nI)...
・1.59/+” dye (IV)
...0.75g/m" gelatin
...6.09/m" Polymethyl methacrylate matting agent...30u/m' (average particle size 0.4μra
and 3.2μff1) glyoxal
...20B/m" Dye (I[) bυ3Na Dye (III), ([V) Organopolysiloxane and polymer hardener were changed as shown in Table 2, but the above sample 2-No.

Samples (Samples 2-No, 2 to No. 5) were prepared in the same manner as in 1, and comparisons were made using a comparative hardener containing either or both of organopolysiloxane and polymer hardener. Sample (Sample 2 No. 6 to No. 10)
was created.

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.

Processing process Development 30℃ 45 seconds fixation
25℃ 35 seconds water washing 15℃
Dry for 35 seconds 45°C 20 seconds Developer Phenidone 0.49 methol 5° Hydroquinone
19 Anhydrous sodium sulfite
609 Hydrous sodium carbonate
5495-nitroimidazole 1000
m9 Potassium Bromide 2.59 Add water to bring the solution to 000 m12 and adjust the pH to 10.20.

Fixer (Part A) Ammonium Thiosulfate 1709 Sodium Sulfite 15g Boric Acid
6.59 Glacial acetic acid
12m12 Sodium citrate (dihydrate)
Add 2.59 water and finish to 275 m (!).

(Part B) Aluminum sulfate 15998% sulfuric acid 2.59 Add water and 4
0rn(finish to l.

When using Part A: 275III2, Part B: 4
Add water to Gmi2 to make lQ.

From Table 2, it can be seen that the present invention also applies to Example 1 in X-ray photosensitive materials.
It turns out that it is equally effective.

Example 3 Each layer having the composition shown below was sequentially formed on both sides of an undercoated polyethylene terephthalate support from the support side to obtain plate-making photosensitive material sample 3-No.1.

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

1st layer: Emulsion layer average grain size 0.2 μm, 8 g containing 24 mol% of HegBr
Amount of silver coated with emulsion consisting of Ilct'...4.0g7m2
4-Hydroxy-6-methyl-1,3,3a,7-chitrazaindene...0.6g Polyoxyethylene nonylphenyl ether -50mg/m2
Gelatin...2.5g/m2
2nd layer; Protective layer gelatin...1.0g/l
112 Polymethyl methacrylate particles...50I
I1g/+l12 (average particle size 3-4 μm) Mucochlor flu-15B/
m2 organopolysiloxane...0.8y
/m2 Polymer sister 1 imitation ・・・6xlO' equivalent/10
0g gelatin back 1st layer dyed 1”1(V)...40
0g/l112 dye rE't (V[)
・=8.6g/m2 Dye II (■)
...500FI/l112 gelatin ...1g/m2 Styrene-maleic acid copolymer ...20B/m25-
Nitroindazole...8+H/m2
Clyoxal...4mg/m2
Back 2nd layer polymethyl methacrylate-1/particles...35 g/
l112 (average particle size 3.0.8μ and 0.4μ) Ceratin...h/...2 Glyoxal...20m/1I12
Mucochloric acid...10IIll
F/II + 2 pieces 1 fidal cylinder force alumina...
・300+ay/m2 (manufactured by Du Pant, Lud
ox^M) Some f'! (V) Dye (Vl) Dye (■) The samples were treated under the conditions shown below, and the slip properties, transfer properties, sensitivity and fog were measured in the same manner as in Example I.

Processing conditions Development 29℃ 30 seconds fixation
28℃ 20 seconds water washing 20℃
Dry for 20 seconds at 45°C for 30 seconds. Potassium bromide 2.5g Ethylenediamine 4l'tF M disodium! S potassium sulfite (55% aqueous solution) 90m + 1 potassium carbonate 25g hydroquinone
1035-Methylbenzotriazole 100+ng5-nitrobenzotriazole
100g 1-phenyl-5-merca-11-tetrazole 30IlllF 5-2L loimidazole 50Il1g
1-phenyl-4-methyl-4-hydroxymethyl-2(-pyrazolidone O1 group diethylene glycol 60g sulfur and lithium hydroxide Add enough water to bring the pH to 10.6 by 3AM, 5
Finished to 00m1. (pH 10.6) When used, the above stock solution is diluted twice with water.

Fixer (bar 1-A) Ammonium thiosulfate 170g Sodium sulfite 15° Boric acid
6.5g glacial acetic acid
12IIll que〉'acid sodium (dihydrate) 2.5F! Add water to make it 275+++1.

(Bert B) Aluminum sulfate (18 hydrate) 15FI9
Add 8% sulfuric acid 2.5g water to make 40ml.

The method for adjusting the liquid used is to add about 600+ai' of water to 275 mf of the above Virt A, then add 40 ml of Virt B, and then add water to make 11.

The measurement results are shown in Table 3.

Table 3 shows that the present invention is also effective in silver halide photographic materials for plate making.

〔Effect of the invention〕

According to the present invention, the transferability of organopolysiloxane is improved without deterioration of photographic performance when the outermost hydrophilic colloid layer of a photographic light-sensitive material contains an amount of organopolysiloxane that provides sufficient slipperiness. Ru.

Claims (1)

[Claims] In a photographic light-sensitive material having at least one hydrophilic colloid layer on the outermost surface on a support, at least one of the hydrophilic colloid layers on the outermost surface contains an organopolysiloxane and is hardened with a polymeric hardener. A photographic material characterized by being coated with a film.