JPH0648355B2 - Silver halide photographic light-sensitive material - Google Patents

Description

The present invention relates to a photographic light-sensitive material having improved physical properties, and particularly to a surfactant having an aliphatic hydrocarbon group and a sulfate ester group or a sulfonic acid group in the molecule. The present invention relates to a photographic light-sensitive material having improved sliding characteristics due to the presence of C. in the back surface layer.

"Conventional technology" Photographic photosensitive materials are manufactured during coating, drying, processing
When handling such as winding, rewinding or conveying during use such as photography, development processing, printing, projection, etc., photographic sensitive material such as contact friction with various substances or between the sensitive material surface and the back surface. Contact friction between them is often undesirably affected. For example, scratches and abrasions on the surface or back surface of the photosensitive material, deterioration of drivability of the photosensitive material in a camera or a projector, and generation of film scraps.

To increase the scratch resistance of the photographic constituent layers of the photographic light-sensitive material,
By reducing the sliding friction of the photographic light-sensitive material, it is possible to obtain a photographic light-sensitive material with improved physical properties that allows the gates of film magazines, camera gates, projector gates, etc. to move smoothly without damaging the photographic material. Various methods have been proposed in the past. For example, a method of adding certain gelatin hardeners to photographic constituent layers to increase scratch resistance, as described in British Patent No. 1270578, photographic emulsions as described in US Pat. No. 3,042,522. A method of imparting slipperiness to a photographic film by simultaneously containing dimethyl silicone and a specific surfactant in a layer or a protective layer, dimethyl silicone on the back surface of a photographic film base as described in US Pat. No. 3,080,317. And a mixture of diphenyl silicone and British Patent No. 1
A method for imparting slipperiness by coating a fatty acid ester of a polyhydric alcohol as described in US Pat. No. 4,663,304 and a higher alcohol ester of a higher fatty acid described in US Pat. No. 3,121,060 and JP-B-58-33541. For example, a method described in British Patent No. 1143118 in which a protective layer contains a methylphenyl silicone having a triphenyl terminal block to impart a slip property to a photographic film is known.

Also, U.S. Pat. No. 2,732,305 and Japanese Patent Publication No. 43-13
As described in Japanese Patent Publication No. 499, a method is known in which an organic carboxylic acid amide is added to an anti-halation layer made of an alkali-soluble resin provided on the surface of a base back to prevent transfer of the anti-halation layer to the emulsion surface.

"Problems to be solved by the invention" However, when these known methods are used to improve the running property of a photographic film in a camera, for example, when it is applied to a base back layer, the slipperiness (friction coefficient) is surely high. However, when actually passing through the camera, the runnability was not improved, and even if it improved, powder was deposited on the surface of the base back, and uneven coating etc. at the time of coating the photographic emulsion It often has an effect or an unfavorable phenomenon.

An object of the present invention is to provide a photographic light-sensitive material having improved runnability of a photographic film in a camera without precipitation of these powders and without impairing coatability of a photographic emulsion.

"Means for Solving Problems" The object of the present invention is to provide an organic solvent-soluble cellulose ester in the back layer of a photographic light-sensitive material, the following general formula (I), or
It was achieved by the presence of a surfactant represented by (II).

General formula (I) RA _n OSO ₃ M General formula (II) R _n SO ₃ M In the formula, R represents an alkyl group having 14 to 22 carbon atoms, an alkenyl group or a substituted alkyl group, and A represents a divalent group. , M
Represents a cation. n represents 0 or 1. The carbon number of R is preferably 14-18.

And so on.

Examples of M include Na, K, Li, Mg, Ca, Ba and NH ₄ , HN (CH ₃ ) ₃ , HN (C ₂ H ₅ ) _{3 and the} like.

Next, specific examples of typical compounds used in the present invention are shown.

_{NO.1 C 14 H 29 OSO 3 Na} NO.2 C 16 H 33 OSO 3 Na NO.3 C 18 H 37 OSO 3 Na NO.4 (C 16 H 33 OSO 3) 2 Mg NO.5 C 16 H 33 OSO ₃ HN (C ₂ H ₅ ) ₃ NO.6 NO.7 NO.8 C ₁₆ H ₃₃ OCH ₂ CH ₂ OSO ₃ Na NO. 9 The average of n is 2.

NO.10 NO.11 C ₁₄ H ₂₉ O (CH ₂ ) ₄ SO ₃ Na NO.12 C ₁₆ H ₃₁ NHCH ₂ CH ₂ SO ₃ Na NO.13 C ₁₄ H ₂₉ SO ₃ Na NO.14 NO.15 CH ₃ (CH ₂ ) ₁₁ CH = CHSO ₃ Na NO.16 NO.17 NO.18 NO.19 C ₂₂ H ₄₅ OSO ₃ Na The above compound used in the present invention can be easily synthesized by a usual method.

For example, sodium hexadecyl sulphate is prepared by dissolving hexadecyl alcohol in methychlor, adding 10% excess chlorosulfonic acid to the alcohol at about 10 ° C, and then reacting at the same temperature for 1 hour and at 20 to 25 ° C for 1 hour. After that, neutralize with 50% aqueous NaOH solution. After distilling off the solvent Methyl chloride, ethanol was added to dissolve it to remove the insoluble inorganic salt, and the product was crystallized by cooling with ice. Also, some of the compounds used in the present invention are commercially available.

The fact that the compounds used in the present invention are extremely excellent for the purposes of the present invention will be explained in detail in the examples below. For example, many of the well-known dimethyl silicones of the present invention are It shows the same sliding performance as the compound, but generally has a serious drawback that adversely affects emulsion coating.
Further, higher fatty acid esters and amides often have insufficient sliding performance, and in many cases, precipitation of powder is observed on the film surface over time.

The reason why the compound of the present invention is superior in these points is probably because the surface orientation is in a preferable state.

In the practice of the present invention, various coating solutions for forming a back layer of a photographic light-sensitive material, the compound used in the present invention is water,
Either a method of dissolving in an organic solvent or a mixed solvent thereof and then adding and coating, or a method of overcoating or permeating the protective layer is used.

The amount of the compound used in the present invention is not particularly limited, but 5 to 500 mg, especially 1
It is preferably 0 to 100 mg. The thickness of the back layer is preferably in the range of 0.01 to 10 μm, particularly preferably 0.1 to 2 μm.

In applying the compound of the present invention to the base back surface, preferred binders having a film-forming ability used together are cellulose triacetate, cellulose diacetate, cellulose acetate maleate, cellulose acetate phthalate, hydroxyalkylalkyl cellulose phthalate (alkyl). Cellulose ester such as group having 1 to 4 carbon atoms, hydroxyalkylalkyl cellulose tetrahydrophthalate (alkyl group having 1 to 4 carbon atoms), hydroxyalkylalkyl hexahydrophthalate (alkyl group having 1 to 4 carbon atoms), etc. Polycondensates of formaldehyde and cresol, salicylic acid or oxyphenylacetic acid, or terephthalic acid or isophthalic acid and polyalkylene glycol (ethylene glycol Polycondensation polymers such as polycondensates of propylene glycol with di, tri, tetramers); homopolymers of acrylic acid, methacrylic acid, styrenecarboxylic acid or styrenesulfonic acid, or monomers or maleic anhydride thereof. And styrene derivatives, alkyl acrylates (where the alkyl group is carbon 1
4), alkyl methacrylate (alkyl group has 1 to 4 carbon atoms), vinyl chloride, vinyl acetate, alkyl vinyl ether (alkyl group has 1 to 4 carbon atoms) or copolymer with acrylonitrile, or ring-opening half-esters thereof. Alternatively, there are synthetic polymers such as homo- or copolymers obtained from monomers having a polymerizable unsaturated bond such as semi-amides, partially hydrolyzed polyvinyl acetate and polyvinyl alcohol. Further, an organic solvent-soluble binder is preferably used.

When a binder is used, water, an organic solvent or a mixture thereof can be used as a solvent, but an organic solvent is preferably used. Both the above-mentioned organic solvents and the organic solvents mentioned here include the following solvents. Examples of such a solvent include alcohols such as methanol, ethanol and butanol, and ketones such as acetone and methyl ethyl ketone. Halogenated hydrocarbons such as methylene chloride, carbon tetrachloride and chloroform, ethers such as diethyl ether, dioxane and tetrahydrofuran, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic carbonization such as cyclopentane and cyclohexane. Examples include hydrogens, aliphatic hydrocarbons such as n-hexane and n-ethane.

In the photographic light-sensitive material of the present invention, any of those usually used as a support for a photographic light-sensitive material can be used. For example, there are cellulose acetate film, acerose acetate butyrate film, polystyrene film, polyethylene terephthalate film, other laminated materials thereof, paper and the like. Variator or α-olefin polymer, especially polyethylene, polypropylene, etc. 2 to 1 carbon atoms
Examples include paper coated or laminated with a 0-polymer of α-olefin.

Various hydrophilic colloids are used in the photographic light-sensitive material of the present invention. Examples of hydrophilic colloids used as a binder for photographic emulsions and / or other photographic constituent layers include gelatin, colloidal albumin, casein, and carboxymethyl. Cellulose, hydroxyethyl cellulose and other cellulose derivatives, agar, sodium alginate, starch derivatives and other sugar derivatives, synthetic hydrophilic colloids such as polyvinyl alcohol, poly N-vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamides or derivatives thereof.・
Partial hydrolysates and the like can be mentioned. If desired, compatible mixtures of two or more of these colloids are used.

The most commonly used of these is gelatin.

In the photographic emulsion layer and other layers used in the present invention, a synthetic polymer compound, for example, a latex-type water-dispersed vinyl compound polymer, particularly a compound which increases the dimensional stability of a photographic material, is used alone or as a mixture (different types). Polymers) or in combination with these hydrophilic, water-permeable colloids. There are many polymers, for example US Pat. Nos. 2,376,005 and 2,739,137.
No. 2,853,457, No. 3,062,674
No. 3, 3,411,911, 3,488,708
Issue 3, Issue 3,525,620, Issue 3,635,715
Issue 3, Issue 607,290, Issue 3,645,740
No., British Patent Nos. 1,186,699, 1,30
7, 373 and the like. Among them, alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, sulfoalkyl acrylate, sulfoalkyl methane acrylate, glycidyl acrylate, glycidyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, alkoxyalkyl acrylate,
Alkoxy methacrylate, styrene, butadiene,
A copolymer or homopolymer selected from vinyl chloride, vinylidene chloride, maleic anhydride, and itaconic anhydride is generally used.

Hardening of the photographic emulsion and / or other photographic constituent layers can be carried out by a conventional method. Examples of the curing agent include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3. , 5-triazine and other U.S. Pat. Nos. 3,288,775 and 2,732,303. British Patent No. 974,723,
Compounds having a reactive halogen, such as divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1, as shown in No. 1,167,207.
3,5-triazine and others US Pat. No. 3,635,35
No. 718, No. 3,232,763, No. 3,49
Nos. 0,911, 3,642,486, British Patent 994,869, and the like, compounds having a reactive olefin, N-hydroxymethylphthalimide, and other US Pat. N-methylol compounds as shown in US Pat. Nos. 732,316 and 2,586,168, isocyanates as shown in US Pat. No. 3,103,437, US Pat. Three
Aziridine compounds such as those shown in US Pat. No. 2,7,280, and No. 2,983,611.
25,294, 2,725,295 and the like, acid derivatives as shown in US Pat. No. 3,100,70.
Carbodiimide compounds as shown in US Pat. No. 4, etc., epoxy compounds as shown in US Pat. No. 3,091,537, US Pat. No. 3,321,3
13 and 3,543,292, isoxazole compounds, halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, or inorganic hard films. Examples of the agent include chrome alum and zirconium sulfate. Instead of the above compounds, precursors in the form of precursors, for example, alkali metal bisulfide aldehyde adducts, methylol derivatives of hydantoin, primary fatty acid nitroalcohols, etc. may be used.

A silver halide photographic emulsion is usually a water-soluble silver salt (eg silver nitrate) solution and a water-soluble halogen salt (eg potassium bromide).
It is prepared by mixing with a solution in the presence of an aqueous polymer solution such as gelatin. As this silver halide, in addition to silver chloride and silver bromide, mixed silver halide such as chlorobromide,
Iodobromide, silver chloroiodobromide and the like can be used.

Various compounds can be added to the above photographic emulsion in order to prevent the deterioration of sensitivity and the occurrence of fog during the manufacturing process of the light-sensitive material, during storage or during processing. Those compounds are 4-hydroxy-6-methyl-1,3,3a, tetrazaindene, 3-methyl-benzothiazole, 1-phenyl-5.
-Many complex compounds such as mercaptotetrazole, many complex compounds, mercury-containing compounds, mercapto compounds and metal salts have been known for a long time.

The silver halide emulsion can be chemically sensitized by a conventional method. Examples of the chemical sensitizer include gold compounds such as chloroauric acid salts and gold trichloride, types of noble metals such as platinum, palladium, iridium, rhodium, and ruthenium, and sulfur compounds that react with silver salts to form silver sulfide. , Stannous salts, amines, and other reducing substances.

If necessary, the photographic emulsion can be spectrally sensitized or supersensitized by using cyanine dyes such as cyanine, merocyanine and carbocyanine alone or in combination, or by using them in combination with a styryl dye.

The photographic light-sensitive material of the present invention contains a bleaching agent such as stilbene, triazine, oxazole and coumarin compounds in the non-light-sensitive photographic constituent layer; : Various photographic filter dyes known as a light absorber may be contained.

Other than the compounds used in the present invention, if necessary, as other sliding agents or adhesive preventive agents, for example, US Pat.
No. 32305, No. 4042399, No. 3121060
And fatty acids with amides or esters and polyesters as described in U.S. Pat. No. 1,466,304 and U.S. Pat. Nos. 1,320,564 and 1,32.
0,565, water insoluble materials as described in U.S. Pat. No. 3,121,060 and U.S. Pat. No. 3,6.
Surfactants such as those described in US Pat. No. 17,286 can be included. There is a limit to the amount of these lubricants other than the present invention to be used, and it is 1: 1 or less by weight with respect to the lubricant of the present invention. Further, as a matting agent, silica having an appropriate particle diameter, an inorganic compound such as strontium barium sulfate, an organic polymer such as polymethylmethacrylate, or polystyrene can be contained.

The photographic light-sensitive material of the present invention can be applied to photographic constituent layers such as a photographic emulsion layer, especially to an antistatic layer provided on the outermost side of a photographic light-sensitive material.
5,297, 2,972.537, 2,97
No. 2,538, No. 3.033,679, No. 3,07
2,484, 3,262,807, 3,52
No. 5,621, No. 3,615, 531, No. 3,63
0,743, 3,653,906, 3,65
Hydrophilic limers, such as those described in US Pat. Nos. 5,384,3,655,386, and British Patents 1,222,154, 1,235,075, are described, for example, in US Pat. No. 263, 2,976, 148, and a hydrophobic polymer as described in, for example, US Pat. Nos. 2,584,362 and 2,591,590. Compounds are prepared, for example, in US Pat. Nos. 2,639,234 and 2,649,372.
Nos. 3,201,251 and 3,457,076, sulfonic acid type anionic compounds as described in, for example, U.S. Pat. Nos. 3,317,344 and 3,51.
Phosphate esters and quaternary ammonium salts as described in US Pat. No. 4,291.
2,157, 2,982,651, 3,39
9,995, 3,549,369, 3,56
Cationic compounds as described in U.S. Pat. No. 4,043, eg nonionic compounds such as those described in U.S. Pat. No. 3,625,695, such as U.S. Pat. No. 3,736,268. Amphoteric compounds such as those described in US Pat. No. 2,647,836
Complex compounds such as those described in US Pat. No. 2,717,834 and US Pat. No. 3,655,387 may include organic salts.

The compound of the present invention can be applied to all kinds of photographic light-sensitive materials regardless of black and white or color.

The silver halide emulsion contains an ortho emulsion, a panchromatic emulsion, an infrared ray emulsion, an X-ray or other invisible light recording emulsion, a color photographic emulsion such as an emulsion containing a color-forming coupler, an emulsion containing a dye developing agent and a bleachable dye. And various silver halide photographic emulsions such as emulsions.

The color photographic emulsion may contain 2 equivalents or 4 equivalents of a color forming coupler. For example, open-chain type ketomethylene yellow-forming couplers such as benzoylacetanilide type or pivaloylacetanilide type, magenta color forming couplers such as pyrazolone type or indazolone type, and cyan forming couplers such as phenol type or naphthol type are preferably used. For example
No. 18256, a yellow coupler represented by the general formula [I], a magenta coupler described in JP-B-48-38416, a cyan coupler described in JP-A-48-42732, and U.S. Pat. No. 2,428,054. 2,449,
966, 2,455,170, 2,600,7
88, 2,983,608, 3,148,06
No. 2, etc., colored couplers, US Pat. No. 3,22.
The release-inhibiting coupler described in No. 7,554 can be used.

"Examples" Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. In addition, the addition amount "part" in an Example represents a weight part.

Example 1 A coating solution for a backing layer having the composition shown in Table 1 below was applied onto a triacetyl cellulose photographic film support and dried (dried at 90 ° C. for 3 minutes) to give a backing layer having a dry film thickness of 0.2 μm. Was formed.

In addition to the compounds of the present invention, for comparison, comparative compounds (A), (B) and (C) shown below were used to form a back layer in the same manner.

Comparative compound (A) Comparative compound (B) C ₁₅ H ₃₁ COOC ₁₆ H ₃₃ Comparative compound (C) C ₂₁ H ₄₃ CONH _{2 An} undercoat layer is provided on the opposite side of the above seven base back layers, and an anti-halation layer and a red-sensitive emulsion are provided thereon. Layer, gelatin intermediate layer, green sensitive emulsion layer, yellow filter layer, blue sensitive emulsion layer, and protective layer, which are coated in this order, and the corresponding color negative film for movies 1-1, 1-2, 1-3, 1 -4, 1-5, 1-
6, 1-7 were obtained. The red-sensitive and green-sensitive emulsions used were silver iodobromide emulsions containing 6 mol% iodine, and the blue-sensitive emulsions used were silver iodide emulsions containing 8 mol% iodine.

These films were cut to a width of about 35 mm, which had been aged for 1 week at 25 ° C. and 60% RH, to obtain 400-film roll-shaped films.

The test items are (1) suitability for application to the support after application, (2) measurement of coefficient of static friction, (3) corresponding to practical skill when pulling out the film from between the aperture plate and the plate plate of the camera. The resistance (corresponding to the running performance of the camera during photographing) was measured and (4) the amount of powder deposited on the surface of the backing layer of the film aged for 7 days at 25 ° C. and 80% RH was visually observed.

The evaluation methods (1) to (3) will be further shown below. The results are shown in Table 2.

(1) Applicability of coating solution to support A coating solution for the antihalation layer and a coating solution in the red-sensitive emulsion layer are formed on a support having an undercoat layer on the opposite side of the base back layer, and a gelatin intermediate layer. The coating solution for layers is applied at a conveying speed of 80 m / min, and the dry bulb temperature is 35 ° C and the wet bulb temperature is 18 ° C
An intermediate product of the color negative film for movies was dried. The surface of the obtained intermediate product was visually observed with reflected light.

Evaluation No coating unevenness: ○ Very weak coating unevenness: △ Coating unevenness: × Many coating unevenness: × × (2) Static friction coefficient measurement method T.Anvelt, JFCarroll, JR., And L.J.Sugden J.SMPTE, 8
The maximum static friction coefficient of the film back surface was determined using the paper clip method described in No. 0 (9) 734 to 739 (1971).

(3) Pull-out resistance measurement Camera aperture plate and press plate (ARNOLD & RICHTER ARRIFLEX 35II on the moving table)
Fix A). After inserting the sample between the aperture plate and the plate and fixing one end of the sample to the load cell, move the moving table at 10 m / min,
The maximum frictional resistance of the film generated at that time was calculated.

As is clear from Table 2, the addition of the compound of the present invention significantly improves the sliding performance. Further, there was no unevenness during coating of the emulsion and no precipitation of powder was observed.

On the other hand, when the comparative compound (A) was used, coating unevenness was remarkably generated during emulsion coating.

Further, when the comparative compound (B) was used, the sliding performance was not so improved.

When the comparative compound (C) was used, the precipitation of powder was remarkably observed on the surface of the base back.

Example 2 A coating solution for a flash layer having the following composition shown in the third example was applied onto a triacetyl cellulose photographic film support and dried (90
(Drying at 3 ° C. for 3 minutes) to form a back layer having a dry film thickness of 0.7 μm.

The same film color negative emulsion as in Example 1 was coated on the opposite sides of these base back layers to obtain films 2-1, 2-2- and 2-3, respectively. The same test as in Example 1
(2) to (4) were performed and the results shown in Table 4 below were obtained.

From the results shown in Table 4, it can be seen that the film 2-2 of the present invention has remarkably improved sliding performance and that no powder is deposited.

Example 3 Antistatic agents (D), (E) and (F) were coated on a triacetylcellulose photographic film support using the coating solutions for backing layers shown in Table 5 below and dried (70
After drying at 0 ° C. for 1 minute), bases 3-1, 3-2-, 3-3 provided with a back layer having a dry film thickness of 0.2 μ were prepared.

Antistatic agent (D) Antistatic agent (E) Antistatic agent (F) The base coating solution used for the base 2-2 shown in Example 2 was overcoated on these bases and dried (90
Dried at 3 ° C for 3 minutes) and dried film thickness of 0.7μ
Bases 1, 4-2 and 4-3 were created. Films 4-1, 4-2, and 4- were coated on the opposite sides of these base back layers with the same color negative emulsion for motion picture as in Example 1, respectively.
Got 3. The same tests (2) to (4) as in Example 1 were performed, and the results shown in Table 6 below were obtained.

From Table 6, each of the films (4-1, 4-2, 4-3) has the same sliding performance as the film (2-2) shown in Example 2, and the deposition of powder is also recognized. Nakatsuta.

Example 4 A back layer coating solution having the composition shown in Table 7 below was coated on a triacetyl cellulose photographic film support (9
After drying for 3 minutes at 0 ° C., a halation prevention layer having a dry film thickness of 1 μ was formed.

The color negative emulsion for kinema was coated on the opposite side of these base back layers to form films 5-1 and 5-2, respectively.
5-3 was obtained. Tests (2) to (4) were conducted on these films in the same manner as in Example 1, and the results shown in Table 8 were obtained.

From the results shown in Table 8, it can be seen that the film 5-2 of the present invention has remarkably improved sliding performance and has no powder deposition.

Example 5 A coating solution for a backing layer having the composition shown in Table 9 below was further applied onto the anti-halation layer of the base 5-1 shown in Example 4 and dried (dried at 90 ° C. for 3 minutes). Bases 6-1, 6-2, and 6-3 provided with layers having a dry film thickness of 0.2 μ were prepared.

Kinema color negative emulsions were coated on the opposite sides of these base back layers to form films 6-1, 6-2 and 6 respectively.
-3 was obtained. Tests (2) to (4) were conducted on these films in the same manner as in Example 1 and the results shown in Table 10 were obtained.

From Table 10, it can be seen that the film 6-2 of the present invention has remarkably good sliding performance and no powder deposition.

Continuation of front page (56) Reference JP-A-53-21922 (JP, A) JP-A-57-11341 (JP, A) JP-B-45-33466 (JP, B1) JP-B-46-43428 (JP , B1)

Claims (1)

[Claims] 1. A photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein an organic solvent-soluble cellulose ester is contained in a back layer of the photographic light-sensitive material.
A silver halide photographic light-sensitive material comprising a compound represented by the following general formula (I) or (II). General formula (I) RA _n OSO ₃ M General formula (II) R _n SO ₃ M In the formula, R represents an alkyl group or an alkenyl group having 14 to 22 carbon atoms, A represents a divalent group, and M represents Represents a cation. n represents 0 or 1.