JPS60140342A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To reduce sliding friction by forming one or more silver halide emulsion layers on a support and incorporating a specified liquid organopolysiloxane and its polymer in at least one of said layers. CONSTITUTION:A silver halide photosensitive material is prepared by forming on a support, one or more silver halide emulsion layers, at least one of them contg. liquid organopolysiloxane or a polymer having siloxane units each represented by general formula I in which R is 1-20C optionally substd. alkyl, aryl, or cycloalkyl; A is a bivalent group; and B is active vinyl, epoxy, methanesulfonic acid, active halogen, active ester, aldehyde, acid halide, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a photographic material with improved physical properties, in particular due to the presence of a liquid polyorganosiloxane and a polymer comprising a siloxane unit having an active reactive group.
The present invention relates to a photographic light-sensitive material which does not adversely affect the coating properties during the production of the photographic light-sensitive material and has improved gliding properties even after development processing.

(Prior Art) Photographic materials generally include a support such as glass, paper, plastic film, or paper coated with plastic, a light-sensitive photographic emulsion layer, and optionally an intermediate layer, a protective layer, etc.
Various combinations of constituent layers of photographic light-sensitive materials such as a back layer, antino-regio 7 layer, and an antistatic layer are coated. Photographic light-sensitive materials undergo various processes during manufacturing processes such as coating, drying, and processing, as well as during handling such as winding, rolling, and unwinding during photographing, developing, printing, and projection. Due to contact friction between parts of devices, machines, cameras, etc. that come in contact with photosensitive materials, or between dust, fiber debris, and other deposits, or contact friction between photographic photosensitive materials, such as between the surface and back surface of the photosensitive material. This often results in undesirable effects, such as scratches or abrasions on the surface or back of the photosensitive material, deterioration of the drivability of the photosensitive material in cameras and other devices, and the generation of film waste in cameras and other devices. etc.

Photographic light-sensitive materials (1) can be used for camera gates such as film magazines, camera gates, projector gates, and printing gates by increasing the restraining strength of the constituent layers or by completely reducing the sliding friction of the photographic light-sensitive material. Various methods have been proposed to date for obtaining 7c photographic materials with improved physical properties that allow the constituent layers to move freely without being damaged. For example, a method of imparting slipperiness to a photographic film by simultaneously containing dimethyl silicone and a specific surfactant in a photographic emulsion layer or a protective layer as described in U.S. Pat. Patent No. 30103,17
A method of imparting slipperiness by providing a mixture of dimethyl silicone and diphenyl silicone on the back surface of a photographic film base as described in the above issue, and a method of adding methylphenyl silicone with a triphenyl end block to the reinforcing layer. The method described in U.S. Pat. No. 1/371I, which imparts slipperiness to photographic films, or the method of imparting slipperiness to photographic films by incorporating di-lower alkyl silicone and β-alanine surfactant into a photographic emulsion or other hydrocolloid layer. Known examples include the method described in U.S. Pat.

However, when attempting to improve the physical properties of photographic light-sensitive materials using these known methods, while they slightly improve the slipperiness and other properties, they do not completely eliminate the tackiness of the film surface. , Since the effect of imparting slipperiness to the silicone used is weak, the amount of silicone required to impart good slipperiness to the photographic film requires the use of multiple layers, which has an adverse effect on the coating properties during the production of photographic light-sensitive materials.
In order to provide a remarkable liquid repellency that interferes with the development process, or to obtain a photographic film with practically favorable physical properties using di-lower alkyl or diphenyl silicone, it is necessary to use a mixture of surfactants with a limited structure. There were some drawbacks, such as being forced to.

In addition, in order to improve these drawbacks, Tokuko Sho! uses a liquid organopolysiloxane having an alkyl group with one or more carbon atoms. There is also a method described in US Pat. No. 1,101,172 SR which uses an alkylpolysiloxane having a polyoxyalkylene chain. However, although these methods can be seen to have a considerable improvement effect on certain defects, especially when applied to the pack layer, the added silicone may have an adverse effect during the coating of the photographic emulsion and impair various coating properties. There is. (It is believed that the added silicone migrates to the surface of the support on the side where the photographic emulsion is coated).

In addition, the running properties of the film after the development process on the conveying roller and within the camera were sometimes reduced.

As a method to eliminate the drawback that the slipperiness effect is lost after the development process, recently, US Patent No. 11tlOu,
No. 276 discloses a method using a highly crosslinkable silicone (silicone polycarbinol).

However, when trying to improve the physical properties of photographic materials using this method, although it is true that the slipperiness after development is maintained, the improvement effect is not sufficient in terms of coating properties during the production of photographic materials. It wasn't. In other words, it does not improve the occurrence of so-called coating unevenness, which occurs when a coating solution consisting of a hydrophilic colloid such as a photosensitive emulsion cannot be uniformly coated on a support, which is caused by simultaneous multilayer coating and high speed coating and thin layer coating. Ta.

(Objective of the Invention) The first object of the present invention is to reduce the sliding friction of photographic light-sensitive materials, and to improve the physical properties of camera gates such as film magazines, camera gates, and projector gates so that they can all move smoothly. The purpose is to provide photographic fees.

A second object is to provide a photographic material with improved slip properties without impeding coating properties during the production of photographic materials.

The third object is to provide a photographic photosensitive compound in which the film dried after the phenomenon treatment has good slip properties.

(Structure of the Invention) These objects are to provide a silver halide photographic light-sensitive material having at least one light-sensitive emulsion layer on at least one side of a support. This was achieved by the presence of a polymer and a liquid organopolysiloxane consisting of a siloxane unit having an active reactive group represented by the general formula [I].

General formula [■] 5iO- -B In the formula, R is an alkyl group having a total carbon number of 1 to λO (for example, methyl,
ethyl, propyl, amyl), a substituted alkyl group (eg alkyloxy7'alkyl, arylalkyl, aryloxyalkyl), an aryl group (eg phenyl), a substituted aryl group (eg tolyl) or a cycloalkyl group (eg cyclohexyl).

A is a divalent group (for example, alkylene having a carbon number of λ to 10% substituted alkylene (for example, -CH2C82C1-(2NHCH2CH2-)).

-CH2CH2CH20(CH2CH2()+n(,:
H2CH2-) etc.).

B is -Y-CH=CH2 group (Y is -c: 0-1-N
HC: 0-1 or -S 02-) -CHCH2G
group, (G is a halogen atom, preferably t L < UF, ClT
h-f'), -GOOCH2GM', vinyl group, epoxy group, methanesulfonic acid group, group having active halogen, active ester group, aldehyde group, maleimide group, acid/ride group, azolide group, incyanato group, Represents a methylol group, an acid anhydride, or an ethyleneimine group.

Among the organopolysiloxanes used in the present invention, organopolysiloxanes represented by the following general formula [■] consisting of siloxane units represented by the general formula CI) and dimethylsiloxane units are particularly preferably used.

General formula [II] l: an integer from j to 00, preferably 10 to 100 □・7 to! An integer of O is preferably 1/~, 20 1,000 m = A~1130 A, B are synonymous with general formula (I). There is a way.

One method is to bond a compound with an active reactive group to silane or silicone base, and the other method is to bond a compound with a silane or silicone base having a functional group such as a hydroxyl group, an amino group, or a carboxyl group. This is a method of introducing active reactive groups.

For methods of introducing reactive groups, see, for example, JP-A No. 1-7 G32, J/-/, 2T/2-H, and JP-A No. 1-7. /-4
Specifications of Alt01, British Patent No. 107/Kotaza, U.S. Patent No. 22 Octopus No. 10, etc., Oil Chemistry T Vol.
Reactive groups were introduced with reference to the winding ratio of 44+jj (/73 years) and the like.

In addition, methods for synthesizing compounds having effective substituents for introducing these reactive groups (e.g., hydroxyl group to halogen group (a substitution method, halogen group to 1-mino group substitution method)
For example, Journalof tbe Che
mical 5ociety A11lfi
), same Tata page (1993), same 3110 (/riso
), Journal of NleAmerican
Chemical 5ociety Vol. J4', page 1, Vol. J, Vol. 3/page (/732), Vol. 3 pages, Organic Reaction Volume 5, 7 pages (14A), and Chemistry
There are many known synthesis methods such as Letter, p. 77 (1971). The bonding of compounds with active reactive groups to silicone is shown, for example, in Japanese Patent Publication No. 31-1077/, Tokibu Shogu 3-2♂t9 and Japanese Patent Publication No. Shouj-/4' Zariza. Addition reaction of dimethylpolysiloxane containing SiH groups to olefin ribs (olefins containing actively reactive groups) using a metal catalyst such as
It is easily synthesized by a condensation reaction of dimethylpolysiloxane containing an iOR (R is H or CH3, C2Hs) group and an alcohol (alcohol having an active reactive group) using picoline or the like as a catalyst.

Next, examples of typical liquid organopolysiloxanes will be given, but the present invention is not limited thereto.

l−λj%mζ! ,n-! 0-fCHx CkIzmnCH2CH2SOzC,k
12CIVJI L-i 2j, rn”* j h n
”i jNs*cocn=c)+.

71! =-921% m"; lo ocH2cH20sO2c113 11#+21 mζj I-λOXα m-pirnLi30 I CH() mζe31 \1 1-λ1 m-7弘n"i I Synthesis Example-1 (Synthesis of compound j) Synthesis of allyl glycidyl ether 23 λg (t mol) of allyl alcohol is placed in a three-necked flask and 0.01 mol of tin tetrachloride is added thereto.

Next, while stirring octopus and jll (1 mol) of epichlorohydrin, add 30~J! Keep the temperature at 0C and drip. After the addition is complete, continue stirring at the same temperature for about 1 hour. The mixture was further heated and boiled and refluxed for about 2 hours to complete the reaction. α-allyl-α′
-Chlorhydrin ether (yield rig) is obtained.

Place 1 mole of α-allyl-α'-chlorohydrin ether in a three-necked flask and place II-? Addition to j'C λ
1.2 mol of jt% caustic soda aqueous solution was added dropwise over 30 minutes while stirring vigorously, and vigorous stirring was continued for another hour at S~ioo''c.

After the reaction, a small amount of water necessary to dissolve the precipitated inorganic salts is added, and when the mixture is left to cool, it separates into two layers. Scrape the upper layer and dry with anhydrous potassium carbonate. Purify by vacuum fractional distillation.

Allyl glycidyl ether, t) p7J~7j'C/j
Oho Hg, / jJ ~f'C/ 7 r Ov
A yield of 1 g is obtained.

Synthesis of Compound j 1''-=+23% mζj The above-mentioned silicone-1339 having a SiH group is charged into a reaction vessel, and 0.0037/ml of chloroplatinic acid catalyst is added thereto.

Allylglycidylny chill while stirring.

Add Reference I to make 1 reaction mixture! ! Upon heating to 0C an exothermic reaction begins.

Allyl glycidyl ether toy is gradually added dropwise while maintaining the reaction +2λ degrees at approximately θ to θ0C.

``After finishing, continue stirring for one item for 121!1'.

After the reaction, excess allyl glycidyl ether was distilled off under reduced pressure to obtain the desired product.

Incidentally, an alkali treatment was performed to destroy any SiO that might be present.

Synthesis Example-2 (Synthesis of Compound 2) From 6, t, thorium bisulfite (0-3 mol)
Water 4' 00 mt bath Wt 2, β-chloroethanesulfonyl chloride 97. l1l (0, t mol) and water, 2
III Dissolved in me lzeta water t1 sodium tatide +4
Drop t, +y into the same 11# at about 0 uC. After 30 minutes, JO-related sulfuric acid solution 71. Add tgoll dropwise, stir for 1 hour, and then filter. The following silicone 0-CCH2 (:R20-f, R2 and 112UI≠0
A solution prepared by dispersing 3.39 in water/l was added dropwise at 100 (or less) and left to stand for 3 days under refrigeration, followed by condensation under reduced pressure C to obtain the desired product.

Synthesis Example-3 (Synthesis of compound/ Compound-1 obtained in Synthesis Example-2, 4tμ, Ri1(o.

Dissolve 01 mol) in acetonitrile -〇θm/, stir, then acetonitrile! 6.7 g (o, ot mol) of triethylamine dissolved in Omt was added dropwise at 00C,
After the dripping is complete, stir with a room fan for 5 hours.

After filtering out the precipitated triethylamine dove salt,
Concentrate under reduced pressure. After washing with a small amount of water, it was dried to obtain Compound-7.

Synthesis Example-4 (Synthesis of Compound-3) Add 3 oomtK of acetonitrile to a 00ml solution of acrylic acid loridota, /9 (0.1 mol) in acetonitrile-z.
The following dissolved silicone NR2m=/0 329 (0.01 mol) is added dropwise at o'c. After stirring for 7 hours, the solvent and by-produced hydrochloric acid were distilled off under reduced pressure to obtain the desired product.

Synthesis Example-6 (Compound-1) ()H' m = 3 2≠, J, 9 (0.01 mol) in acetonitrile co00
Methanesulfonyl chloride z dissolved in me at lθ0C,
Add tg (o, oz mol) dropwise with stirring.

After the dropwise addition is completed, stirring is continued for 3 hours while maintaining the temperature below 20"C. Next, the mixture is carefully neutralized with a solution of NaOH cofl (0.0 jt mol) in water.

After concentrating the reaction mixture under reduced pressure, 1 liter of water was added. Dispersed in ether 100
Extract with m1K. After drying the organic layer with anhydrous magnesium sulfate, the desired product is obtained by distilling off the ether.

Synthesis Example-6 (Compound-g) NR2rr, = 2゜tat, CoII (0.07 mol) was mixed with acetonitrile! 00
After dissolving in the solution and stirring, add maleic anhydride (1tiCO-2 mol) in several portions.

/H? After continuing stirring for F, acetic anhydride 70wV,
Add anhydrous sodium acetate A311 and boil on a steam bath for 3 minutes.
Heat for 0 minutes.

After distilling off the solvent, it is dispersed in water/l and ether! 00
Extract with m1. After drying the organic layer over anhydrous sodium sulfate, the ether is distilled off to obtain the desired product.

The refractive index of the organopolysiloxane used in the present invention is not particularly limited, but usually the measured value at Zj'C is about /, ll0j to /, t! 10 is suitable,
Preferably, the measured value at 2j'C is in the range of i, ttir to /-jlo. The refractive index is 1. If μOj is smaller or larger than μOj, the applied photographic material (photosensitive material, especially the transparency of the dried photographic material after photographic processing has been carried out) may be used. It may not affect sexuality.

The viscosity of the organopolysiloxane used in the present invention is not particularly limited, and any of the above-mentioned liquid organopolysiloxanes that can be synthesized by a general method can provide the desired effect, but usually the viscosity measured at 2j0C is Approximately -
〇～about 1ooo.

Those exhibiting O centistokes are suitable.

The polymer used in the present invention is not particularly limited, but one type is one that has a functional group that can bond with the reactive silicone of the present invention. For example, hydroxyl group,
It is a polymer with functional groups such as amine groups, carboxyl groups, and phenol groups.

Next, specific examples will be given, but the present invention is not limited thereto.

Popal, polyhydroxymethyl acrylate.

Polyhydroxyethyl acrylate, polyhydroxypropyl methacrylate, polyhydroxymethylstyrene,
Poly-N-methylolure, acrylamide and copolymers thereof.

Cellulose derivatives such as cellulose acetate and cellulose nitrate. Gelate/, starch, dextra/.

Polyaminoethyl acrylamide, polyvinylamineaminemethylstyrene and their copolymers.

Polyacrylic acid, polymethacrylic acid and copolymers thereof.

The above comonomers include all vinyl monomers having α,β-unsaturated bonds. Examples of copolymers include poly(pehydroxyethyl methacrylate-acrylic acid methyl ester), poly(aminoethyl acrylamide-co-acrylic acid methyl ester), poly(acrylic acid-co-acrylic acid methyl ester), and the like.

Other types of polymers used in the present invention may be bonded not directly to the reactive silicones of the present invention, but also via crosslinking groups. Examples include the following reactive polymers.

Examples include methyl vinyl ether/maleic anhydride copolymer and glycidyl acrylate.

The crosslinking agent includes all those having λ or more functional groups, and examples thereof include the following.

Ethylene glycol, pentaerythritol, hegisamethylene diol, resorcinol, glycerol, aminoethyl alcohol, ethylenediamine, diethylenetriamine, triethylenetetramine, succinic acid, glutaric acid, adipic acid, speric acid, sebacic acid, i, to
- decamethylene dicarboxylic acid, etc.

In addition, when the above-mentioned crosslinking agent is present, the polymer used in the present invention does not necessarily need to be bonded to the silicone of the present invention, and the polymer used in the present invention does not necessarily have a functional group, such as polymethyl acrylate or triacetylcellose. It is also effective for polymers such as

However, when the present invention is applied to the back layer, a hydrophobic polymer is preferred as the polymer, but for example, a method of blending a small amount of the above-mentioned hydrophilic polymer with a hydrophobic polymer, or a method of copolymerizing a hydrophilic polymer/hydrophobic borea. It is also useful to use a copolymer with a small proportion of hydrophilic polymer.

In carrying out the present invention, the organopolymer used in the present invention is preliminarily applied to a photosensitive copy (a hydrophilic colloid liquid for forming the surface layer on the emulsion side and/or each F4 yarn fabric liquid for forming the back layer). Siloxane (general formula CI) is dissolved in water, an organic solvent, or a mixture thereof W:Q'J, etc., and then added, or as an aqueous dispersion prepared in advance in the presence of a suitable dispersant such as a surfactant. Is it added and coated on the photographic emulsion layer or on the support, or is each photographic constituent layer on the support? After being coated, it can be overcoated or impregnated. Also, when a crosslinking agent is used in carrying out the present invention, it is added and used together with the organopolysiloxane in the same manner as described above.

In applying the present invention, it is preferable to incorporate the compound into the back layer of the photosensitive material since it is highly effective.

There is no particular restriction on the amount of organopolysiloxane used in the present invention. However, when used as a photographic constituent layer by adding it to a coating solution before being coated on a support, 0.0.2 to 10
(weight) percent, particularly preferably o, i-4, o(
weight) percentages are used. If it is less than 0.02 ξ-cents, it is difficult to obtain the desired effect, and if it is more than 10%, it is economically disadvantageous.

Application or penetration methods include, for example, U.S. Pat. No. 333
Dip methods such as those described in US Pat. No. 5,026, e.g. extrusion methods such as those described in US Pat.
It can be applied or penetrated from the outside by a method such as a spray method as described in No. 47.

The compound of general formula (I) has an amount of about 9.0 + 0.001 to 0.00. jtl is preferably present, and 0.6oj-0,ip is particularly desirable. However, it goes without saying that the above range varies depending on the type, form, or coating method of the photosensitive material used. In applying the compound of general formula (I) to the pack surface, examples of the film-forming binder that can be used include the following, including the above-mentioned polymers. Cellulose esters such as cellulose triacetate, cellulose diacetate, cellulose acetate malate, cellulose acetate phthalate, hydroxyalkyl alkyl cellulose phthalate, etc.; polycondensates of diformaldehyde and cresol, salicylic acid or oxyphenylacetic acid;
or polycondensation polymers such as polycondensates of terephthalic acid or isophthalic acid with polyalkylene glycol; homopolymers of acrylic acid, methacrylic acid, styrene carboxylic acid or styrene sulfonic acid, or monomers thereof or maleic anhydride; styrene derivatives,
Copolymers with alkyl acrylates, alkyl methacrylates, vinyl chloride, vinyl acetate, alkyl vinyl ethers or acrylonitrile or ring-opened half-esters or half-amides thereof, partially hydrolyzed polyvinyl acetate: Polymerizations such as polyvinyl alcohol, etc. There are synthetic polymers such as homo-tfL copolymers obtained from heptamers having sexually unsaturated bonds.

, F inder, water, an organic solvent, or a mixture thereof can be used as the solvent.

Both the aforementioned organic solvents and the organic solvents mentioned herein include the following solvents. Examples of this type of solvent include alcohols such as methanol, ethanol, and butanol; ketones such as acetone and methyl ethyl ketone; halogenated hydrocarbons such as methylene chloride, carbon tetrachloride, and chloroporm; and diethyl ether, dioxane, and tetrahydrofuran. These include aromatic hydrocarbons such as ethers, Hansen, toluene, and xylene.

When the compound of general formula (1) is mixed with the above binder and applied to the pack surface, about 1 to 300% by weight of these binders constituting the back layer,
Good luck, preferably Ko~l! Add O heavy lid percent amount.

The amount of polymer used in the present invention is - o-o per square meter
t-ig, preferably o, or to o3g.

When a crosslinking agent is used in the present invention, it is used in an amount of 0.12 to 20 times, preferably 7 to 10 times, relative to the compound of general formula (1).

The organopolysiloxane used in the present invention can improve physical properties such as pan-pability and scratch resistance without imparting photographic effects (occurrence of capri, desensitization, etc.) to photographic materials. In particular, the great advantage of the present invention is that coating failures during the production of photographic light-sensitive materials often occur when organosilicones, known as photographic slip agents, are applied to the light-sensitive material pack layer. In contrast, when the organopolysiloxane of the present invention is applied, coating failures do not occur at all, and the durability of the film after development remains unchanged.

This means that the surface of the photographic emulsion layer will not be damaged even when subjected to harsh processing using automatic photographic processors under conditions of high pH, high temperature, and high speed, or for repeated projection. This is a particularly important advantage in the production of positive photosensitive materials for motion pictures, which have a high mechanical strength on the film surface.

The organopolysiloxane used in the present invention can impart appropriate slipperiness to the photographic material to which it is applied, and can improve its compatibility under the conditions of use, particularly in motion picture film cameras and projectors. .

The motion picture film obtained by implementing the present invention has good durability and adhesion resistance in a camera, so it has the advantage of being extremely smoothly driven and significantly reducing the noise of the film during use. Also, depending on the type of camera, the stress at the part where the film comes in contact with the moving film may be too sharp and strong, resulting in partial destruction of the photographic emulsion layer and generation of debris inside the camera. The motion picture negative film according to the invention can eliminate such failures.

It is believed that these advantages derive from the active reactive groups of the organopolysiloxanes of the present invention.

That is, the number of active reactive group units can be freely increased or decreased depending on the properties of the polymer used.

It is presumed that the organosiloxane of the present invention and the polymer have a dense network structure.

In the photographic light-sensitive material of the present invention, all those used as supports for ordinary photographic JRg optical materials can be used. Examples include cellulose acetate film, cellulose acetate butyrate film, polystyrene film, polyethylene terephthalate film, other laminates thereof, and paper. Baryta or α-olefin polymers, especially polyethylene, polypropylene, etc. carbon atoms λ ~
By coating or laminating a polymer of α-olefin of IO, a sheet of good quality paper can be obtained.

Various hydrophilic colloids are used in the photographic material of the present invention, and hydrophilic colloids used as binders for photographic emulsions and/or other photographic constituent layers include gelatin, colloidal albumin, casein, Cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, agar, sodium alginate, sugar derivatives such as starch derivatives, synthetic hydrophilic colloids such as polyvinyl alcohol, polyN-vinylpyrrolidone, polyacrylic acid copolymer% polyacrylamide, or these Examples include derivatives and partial hydrolysates of. Compatible mixtures of two or more of these colloids are used if desired.

Among these, gelatin is the most commonly used.

The photographic emulsion layer and other layers used in the present invention contain synthetic polymer compounds, such as latex-like water-dispersed vinyl compound polymers, in particular compounds that increase the dimensional stability of photographic materials, either singly or in combination. They may also be included in combinations of different types of polymers or in combination with hydrophilic, water-permeable colloids.

There are many types of polymers, such as those described in U.S. Pat.
No. 376.001, same, 73, No. 137, same 2,1
! 3.1117, 3,062,6741, 3.
G//, Ri No. 1, same s, a (g.

No. 701, 3. jkot, No. 420, 3.63j, 7
/! No. J, No. 607,290, No. 3゜4≠1,71
No. 10, British Patent No. I, trt, T Tata No. 30
7. , No. 373, etc. Among those listed are alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, sulfoalkyl acrylate, sulfoalkyl methacrylate, glycidyl acrylate, glycidyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, alkoxyalkyl acrylate. , alkoxymethacrylate, styrene, dutadiene, vinyl chloride, vinylidene chloride, maleic anhydride,
and itaconic anhydride, and nine copolymers and this monopolymer are generally used.

Hardening of the photographic emulsion and/or other photographic constituent layers can be carried out according to conventional methods. Examples of curing agents include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclontanedione, bis(,2-chloroethyl urea), and λ-
Hydroxy Hiro 6-dichloro/, 3. ! -) Riazine, and others, U.S. Patent No. 3.2g1,771, U.S. Patent No. 2.
No. 73+2,303, British Patent No. 27≠, No. 7.2j,
Same 1st. /17,207 etc. Compounds containing reactive halogens, divinyl sulfone,! -acederu/, 3-diacryloyl hexahythroa, i
, s-) riazine, et al., U.S. Patent No. 3. tl! ,7
/I No. 3,232.763, No. 3.4490
, 9// No. J, 4≠Co, ≠gt, compounds having reactive olefins such as those shown in British Patent Nos. U, Ir+, N-hydroxymethylphthalimide, Other U.S. Patent No. 2,7j2. J/A No.

U.S. Patent No. 3. lO3,≠37
Incyanates such as those shown in U.S. Patent No. 3,0/7. λto No. 2.273. Aziridine compounds as shown in U.S. Patent Nos. 2.7.2j, 27≠, U.S. Pat. , U.S. Patent No. 3
, 100, 7o4L, epoxy compounds as shown in U.S. Pat. No. 3.0, 337, U.S. Pat. Inoxazole compounds as shown in No. 3I Tahiro 31λ Taco No.
Halogenocarboxaldehydes such as mucochloric acid, dihydroxydiocane.

Dioxane derivatives such as dichlorodioxa/and other inorganic hardeners include chromium brightane, zirconium sulfate, and the like. For example, in place of the above compound, it is in the form of a precursor.

Alkali metal bisulfite aldehyde adducts, methylol derivatives of hydantoin, primary aliphatic ditroalcohols, and the like may also be used.

Silver halide photographic emulsions are usually made from a solution of a water-soluble silver salt (e.g. silver nitrate) and a water-soluble halide salt (e.g. potassium bromide).
It is prepared by mixing a solution with a water-soluble disease molecule solution such as gelatin. As the silver halide, in addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide, silver iodobromide, silver chloroiobromide, etc. can be used.

Various compounds can be added to the above-mentioned photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the light-sensitive material. These compounds are ψ-hydroxy-6-methyl-1°3.3B, 7-chitrazaindene, 3-methyl-benzthiazole, /-phenyl-! -A large number of compounds including mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, mercapto compounds, and metal salts have been known for a long time.

Silver halide emulsions can also be chemically sensitized by conventional methods. Chemical sensitizers include, for example, gold compounds such as chlorauric acid salts and gold trichloride, salts of noble metals such as platinum, palladium, iridium, Pdium, and ruthenium, and those that react with silver salts to form silver sulfide. Examples include sulfur compounds, stannous salts, amines, and other reducing substances.

Photographic emulsions can be spectral sensitized or superchromically sensitized, if necessary, by using cyanine dyes such as cyanine, merocyanine, and carbocyanine alone or in combination, or in combination with styryl dyes, etc. .

The photographic material of the present invention contains brighteners such as stilbene, triazine, oxazole, and coumarin compounds in the non-light-sensitive photographic constituent layer; ultraviolet absorbers such as benzotriazole, thiazolidine, and cinnamic acid ester compounds; : various photographic filter dyes known as light absorbers : optionally as anti-adhesion agents, for example as described in British Patent No. 1. jko0. jt hiro issue, same/, J, 26'
,jA! water-insoluble substances such as those described in U.S. Pat.
゜A/7. Surfactant materials such as those described in μl No. 1 may be included. Further, as a matting agent, inorganic compounds such as silver halogenide, silica, barium strontium sulfate, etc., and polymer latexes such as polymethyl methacrylate, etc., having a suitable particle size can be included.

The photographic light-sensitive material of the present invention is applied as an antistatic agent to the photographic constituent layers including the photographic emulsion layer, particularly to the antistatic layer provided on the outermost side of the photographic system, for example, in U.S. Pat.
! , 2ri No. 7, same λ, ri 7 λ, 33! @, times l, ri72
, No. 136, No. 2゜272.137, No. λ, 972.
! ;3g issue, 3.033. A7 No., J, 07+
2. μl No. 7, 3.26+2. Za07, same J, 1
2! , A, 2/issue, same! , t/j, 33/ issue, same 3,
No. 630.713, J, 613, Riot No. 3. tjj.

3g No. 1, same 3. t, tjt, 31A, and British Patent No. 1.222, /j'1, same l, co 33,07j
Hydrophilic polymers such as those described in U.S. Pat. 73. , lAJ issue, same λ.

7A, /11.11, for example in U.S. Pat. No. 1, Jl'lt, 3
tλ No. 2. ! Biguanide compounds such as those described in U.S. Pat. Aj
9.23V, same, 4<z, j7.2, same j
, 20/, No. 257, 3. ≠17. Sulfonic acid type anionic compounds as described in U.S. Pat. No. 3,3/7,3≠1, U.S. Pat. j/≠, 2
Phosphate esters and secondary ammonium salts such as those described in U.S. Pat.
, / No. 77, same λ.

2zaλ, 1! / issue, 3,3 tata, tata j@5 3, j
Karaonik compounds such as those described in Hiroji, JA, No. 3.56, No. 0113; For example, U.S. Patent No. 3,73t, 24g
Amphoteric compounds such as those described in U.S. Patent No. λ.

For example, complex compounds such as those described in US Pat. No. 2,7/7. J'J4 No. 3
．． Organic salts such as those described in J.T.T.J.R., No. 317, and the like can be included.

The compounds of the present invention can be applied to all kinds of photographic materials, regardless of whether they are black and white or color.

Silver halide emulsions include ortho emulsions, non-ξ-chromatic emulsions, infrared emulsions, emulsions for recording X-rays and other invisible light, emulsions for color photography, such as emulsions containing color-forming couplers, emulsions containing dye developers, and dyes that can be bleached. It includes various silver halogenide photographic emulsions, such as emulsions containing .

Color photographic emulsions may contain color-forming couplers of λ hit-or-lose or conventional color-forming couplers. For example, open-chain ketomethylene yellow-forming couplers such as benzoylacedoanilide or bi/zoroylacedoanilide, magenta color-forming couplers such as pyrazolone or indasilone, and cyan-forming couplers such as phenol or naphthol are preferred. used. For example, Tokuko Showa
t-/l, 2jl, yellow coupler represented by the general formula CI) described in Japanese Patent Application No. 1≠-16 Magenta coupler described in Japanese Patent Application No. 4-76! The cyan coupler described in U.S. Pat. ≠21. Oj≠ issue, same co, l noon 2. ri No. 16, same λ, gjj.

No. 170, same, No. 100,718', same, Riza 3,
colored couplers described in US Patent No. J, 227, 741, etc.
The detachment suppressing coupler described in the above issue can be used.

The present invention will be further explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A coating solution having the following composition was coated on a triacetylcellulose photographic film support and dried (00C for 13 minutes) to form a pack layer.

An undercoat layer is provided on the opposite side of the base-back layer of the J tilt, and an antihalation layer, a red-sensitive emulsion layer, a gelatin intermediate layer, a green-sensitive emulsion layer, a yellow filter layer, an H-pore agent layer, and a protective layer are provided on the undercoat layer. Color negative film for motion pictures coated with different layers in order /-/, /-ko, /-3% /-Hiroshi,
/-j was obtained. The red and green emulsions each contain iodine.
A molarly engaged silver iodobromide emulsion was used. Evening emulsion contains iodine.
A silver iodobromide emulsion containing molar ratio was used.

After aging these films for one week at λz 0c6o*B,N, j! The film was cut into a m/m width to obtain a roll film of μOO feet.

When producing these films, the coating suitability of the photographic emulsion layer and the driving performance of the films in an atmosphere of λz 0C and 606RH were investigated.

The test item is the applicability of the il+ coating solution to the support.

(2) Measuring the coefficient of static friction; (3) Measuring the resistance force when pulling out the film from between the aperture plate and pressure plate of the camera (which corresponds well to the running performance of the camera during shooting), which corresponds to practical skills.

(11) Coating liquid applied to the support On the support with the undercoat layer on the opposite side of the Easpack layer, apply the diagnostic blood for the antihalation layer and the coating liquid for the red-sensitive emulsion layer, and then gelatin. Coating liquid for intermediate layer fOm/min
Coating at a conveyance speed of , dry bulb temperature JJ0C, wet bulb temperature i
An intermediate product of a color negative film for motion pictures was dried at z 0c.

The surface of the obtained intermediate product was observed with the naked eye using reflected light.

Liver value No uneven coating 20 Very weak uneven coating: Uneven coating occurs: × Frequent uneven coating: X× (2) Static friction coefficient measurement method T, Anvelt, J, F, Carroll, JIL,
.

and L, J, Sugden J, SMPTE, 10
The maximum static friction coefficient of the film pack surface was determined using the -t-Parlip method described in (Li) 7J4I to 73 (Li 7/).

(3) Camera aperture plate and pressure plate (ARNOLD & RI C) on the pull-out resistance force measurement moving table]
) Fix ARRIFLEX3tllA) made by 1 company. After a sample was sandwiched between an aperture plate and a pressure plate and one end of the sample was fixed to a load cell, the moving stage was moved at a rate of 10 m/rnin, and the maximum frictional resistance force of the film generated at that time was measured.

+4> vt (elephant processing The treatment was carried out according to the phenomenon treatment process described below.

Processing process temperature time Color development "Elephant Gua 0C3 minutes" Stop 310C 30 seconds Wash with water for 30 seconds Pre-bath 30 seconds Bleach 3 minutes cheap Water washing I 1 minute Fixed arrival time: 2 minutes Wash with water for 2 minutes Stable bath 10 seconds The treatment liquid used had the following composition.

Color developer Sodium hydroxide 2g Sodium sulfite, 29 Potassium bromide 1. y Sodium chloride ig Borax ip Hydroxylamine sulfate Hiroshi I Ethylene diamine tetraacetate λ Sodium λg K-amino 3-methyl-N-ethyl-N-(β-hydroxyethyl) aniline mo/sulfate φg Add water Total amount /1 Fixed bath formaldehyde (37 cm) Added 10 ml of water, total amount /71 The results obtained are shown in Table 2.

As is clear from the results in Table 1, the samples to which the organopolysiloxane of the present invention was added had no coating failures at all, compared to the samples to which the comparative compound was added.

In addition, it can be seen that the strength, friction coefficient after image processing, and pull-out resistance are equal to or better than those of the comparative sample.

% Fr Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment 1939/1999/1997/1996/1000/100000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000 down
No. 1, No. 2, Benefits of invention; Silver halide photographic photoreceptor 3,
Relationship with the case of the person making the amendment Patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52)
0) Fuji Sharan Film Co., Ltd. Contact Address: 106 Tokyo t W'i'r4a 2-] 126 3o Call Fuji η゛ Film Co., Ltd. Tokyo Honban-1 Tel: +406) 2537 4. Subject of amendment Specification 5 We will submit an engraving of the amended statement of contents (with no changes to the contents).

Procedural amendment book Showa! Year j,,”',) rJ:'j' II Mr. Commissioner of the Japan Patent Office 1, Indication of the case: Showa SR, Japanese Patent Application No. 9/J 2, Title of the invention: Silver halide photographic light-sensitive material 3, Amendment Relationship with the case of a person who makes a patent application Address: 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of amendment: Description 1-Detailed Description of the Invention, column 5, Contents of amendment (1), page 1, line 6 Correct "Anj゛Harage" to "Anti-Harage-7".

(2) On page 6/line 1, I-, ie, multi-layer simultaneous coating, high-speed coating, is corrected to ``multi-layer simultaneous coating, high-speed coating''.

(3) Page g, line V, 1 (for example, amend it to ``alniyasialkyl,'' or ``alniyasialkyl.'')

(4) The material is also g page iHj I feel very pressured.

(5) r' on page 73 (4) OCH2CH20S02CH3 lhanawaλtrn#j
I]3/”=en.25 m'-j-J.

(6) No./F page r (71 (J l Tokoko O m”=FJ all "(7) U2 ! ζλO and correct it.　m”＝″ (7) Page 1, line 7 I-Mi SiOJ “Mi S+■jl and correct it.

(8) Page 27 g to line 7 [0.02 to ./0 (weighting/ζ-cent,
Particularly preferably o. i~6.

(Weight)%' to [standard 0.02~300 (city 1ぢ}%,
Particularly preferably, it is corrected as θ,l~·ltaO (deuterium percent).

(9) 27th negative // line [io,’: ``Nice to meet you'' [more than 300 bacent] and correct it.

(II λg page 6th line [, used film formation! 7!i{r- has”) [,
It has the film-forming ability used].

0υ O,, 2 to 20 times, preferably 1 to 20 times the compound [on page 30/line 0]
・It is 70 times larger. ” to 001 to 20 times the reactive group h1 of compound 1,
Preferably, it is /~io times.''

Claims (1)

[Scope of Claims] A photographic light-sensitive material having at least one photographic emulsion layer on a support, wherein at least one of the surface layers of the light-sensitive material has a siloxane unit represented by the following general formula CI). A silver halide photographic material characterized by the presence of a liquid organopolysiloxane and a polymer. General Formula CI] 5iO--B In the formula, %R represents an alkyl group, substituted alkyl group, aryl group, substituted aryl group, or cycloalkyl group having 1-coθ carbon atoms. A represents a divalent group. B is an active vinyl group, an epoxy group, a methanesulfonic acid group,
It represents an active halogen group, active ester group, aldehyde group, acid halide group, azolide group, isocyanate group, methylol group, acid anhydride, ethyleneimine group, or maleimide group.