JPS6190152A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain an image superior in sharpness by laminating on a support a silver halide emulsion layer, and a protective layer contg. a slipping agent, and the reaction product of a gelatin and a hardener having >=3 functional groups in the molecule. CONSTITUTION:The silver halide photosensitive material is obtained by forming one or more silver halide emulsion layers on the support and the protective layer on this layer by coating it with a coating soln. contg. at least one of slipping agents represented by formulae I-IV (each of R1-R6 is 10-20 C alkyl; m is 2, 3, or 4; R7 is an aliphatic or aromatic group; R8 is H or alkyl; R9 is alkyl or the like; and A is a divalent aliphatic group), and a product obtained by reacting the hardener having >=3 functional group in the molecule with the gelatin in an aq. soln.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material (hereinafter simply referred to as a light-sensitive material) having excellent photographic properties and processing properties. The present invention relates to a photosensitive material which has excellent properties, has significantly improved scratch resistance, and is suitable for high-temperature and rapid processing.

[Conventional technology]

In recent years, color photosensitive materials have been pursued to be completely thinner in order to improve image quality, higher sensitivity, and stability during high-temperature rapid processing, and photosensitive materials with a dry film thickness exceeding Iμ are rare. . On the other hand, there is still no substitute for gelatin as a component of photosensitive materials, and it plays a major role in most layers, including photosensitive layers, intermediate layers, and surface layers containing silver halide.

The coating film of a photosensitive material having a constituent layer made of gelatin has a serious drawback in that it has a high coefficient of friction against other metal surfaces or gelatin surfaces, and the surface is easily damaged by contact, friction, etc. Therefore, improving the scratch resistance of the gelatin-containing layer, especially the outermost protective layer, is one of the most difficult techniques for photosensitive material manufacturing engineers.

Various methods have been investigated to increase the scratch resistance of gelatin films. For example, by providing a non-photosensitive protective layer on the outside of the photosensitive emulsion layer and further including a matting agent in the protective layer, the surface of the photosensitive material is roughened, the contact area is reduced, and the friction coefficient is There are methods such as adding a sliding agent to reduce the friction coefficient of the film surface, and adding a hardening agent to crosslink gelatin and harden the film surface.

Although these methods are effective and each have their advantages, they also have associated disadvantages. For example, the use of a matting agent is inferior in terms of preventing scratches, and when used in large quantities, the transparency of the photosensitive material decreases, the decolorization of images is affected, and the retouchability is also deteriorated.

On the other hand, a considerable amount of slipping agent is required to achieve a sufficient effect, and as a result, oily substances may adsorb to the film surface during processing, causing contamination or causing devitrification and deteriorating sharpness. . Furthermore, if an attempt is made to harden gelatin with a hardening agent to the extent that scratches do not occur, the hardening agent will diffuse into the underlying layer, resulting in so-called overhardening, which will have a negative impact on raw temperature photographic properties and processability. As described above, the current situation is that a technology that completely satisfies the physical properties of the film, the low-strength properties, and the processability has not yet been completed.

[Purpose of the invention]

An object of the present invention is to provide a light-sensitive material that has excellent processing stability without impairing photographic properties, and furthermore, to provide a light-sensitive material that has significantly improved scratch resistance.

[Battle bottom of invention]

As a result of various studies on the relationship between the degree of hardening and slipperiness of gelatin films, the present inventors found that a slipping agent is used in the protective layer of a photosensitive material, and a hardening agent that completely blinds three or more functional groups in one molecule. It has been found that all of the above objectives can be achieved by containing gelatin which has been reacted in advance in the form of an aqueous solution.

In the present invention, the protective layer refers to a non-photosensitive surface layer coated on the outer side of the silver halide emulsion layer coated farthest from the support. This protective layer may consist of multiple layers, but
One to two layers are preferred.

The slip agent in the present invention generally refers to an additive that improves slip properties (reduces the coefficient of friction) when added to the uppermost layer of a photosensitive material.

! Although a wide range of slipping agents described in JP-A-52-16224, JP-A-54-159221, JP-A-55-79435, and Japanese Patent Publication No. 58-33541 can be used, the following general formula 1 is preferred as a slipping agent: l-11, I:
1-2), [:I-3] and Cl-4].

General formula [:I-'1] CH,0COR1 CHOCORt CH,0CORs In the formula, R1, R2 and R1 each have 10 to 2 carbon atoms
0 alkyl group.

General formula [I-21 In the formula, R4 represents an alkyl group having 10 to 24 carbon atoms.

ml'j: represents an integer from 2 to 4. The winter melons can be the same or different.

General formula [1-31% formula% In the formula, R1+ and bird each represent an alkyl group having 10 to 20 carbon atoms.

The alkyl groups in general formulas Cl-1), Cl-21 and Cl-31 may be linear or branched, and may be substituted with other atoms or substituents as long as the effects of the present invention are not impaired. may be done.

General formula [:I-4] In the formula, the island represents an aliphatic group or an aryl group, R8 represents a hydrogen atom,
The alkyl group 'k and Re represent an alkyl group or an alkoxyalkyl group. A represents an aliphatic divalent residue. n
is O or an integer from 1 to 12, p is 0 to 50, q is 2 to F, X is O to 100, y is 1 to 50, 2 is a number from O to 100, x + y + z is 5 ~250 numbers.

Representative specific examples of the compounds represented by the general formulas Cl-1], [:I-2], Cl-3) and [:I-4] are listed below. It is not limited by.

(-1CH, 0COC16H, (n) ■-3CH, 0COC1sH,, (n) 1-9
CHs ■ l-14n-CsaHzyCOOC1@[1B(n)I
-15n-Cts I(st C00Cta Haa
(n) I -17n C13HtyCOOC26H4t
(n)I-18n-CtsHatCOOCoH4t(
n) x + y + z = +Xl-y+z = 40 x + y + z = us . OH Disperse to a particle size of 1 to 10μ and O/W.
It can be added by making a type emulsion, or it can be added to the coating solution directly in the presence of a suitable dispersant or after being dissolved and diluted with a suitable organic solvent. The slipping agents according to the present invention may be used in any combination.

These slip agents provide particularly favorable properties when used in a weight ratio of 0.1 to 50% relative to the water-soluble binder, such as gelatin, forming the protective layer.

In the present invention, the above-mentioned hardening agent having three or more functional groups refers to a hydrophilic colloid substance used as a binder in the present invention, especially one molecule of which has a reactive site with gelatin molecules or an active site that causes gelatin molecules to react with each other. It is a compound that has three or more in it. Stone compounds advantageously used as such hardening agents include those having an active vinyl group and those having an active halogen. Therefore, as a hardening agent having three or more active vinyl groups,
For example, U.S. Pat.
Examples include compounds described in Publications No. -44164 and No. 52-21059. As a hardening agent having three or more active halogens, for example, JP-A-53-6306
Compounds described in Publication No. 2 and the like can be mentioned.

Among these, preferable hardening agents having three or more active vinyl groups include the compound group represented by the following general formula (n-1) having three or more acryloyl groups, or the following compound group having three or more vinylsulfonyl groups 'e Examples include a group of compounds represented by the formula [■-21] and the general formula Cll-3:l.

General formula [ll-11R (COCH=CHJ n, where R
represents an n-valent organic residue (for example, an aliphatic residue substituted with NH, a saturated heterocyclic residue), and n represents an integer of 3 or more.

In the general formula CI[-z]x(socu=ca,)nz,
X represents an n'-valent organic residue (for example, an aliphatic, aromatic, alicyclic, or saturated heterocyclic residue), and n' represents an integer of 3 or more.

In the formula, one of R1 and avian represents hydrogen, and the other represents hydrogen or a methyl group. The numbers may be the same or different and represent a divalent bonding group (for example -Nu- or -0-) or a single bond. B represents an m-valent aliphatic residue, an aromatic residue, or a saturated heterocyclic group which may be interrupted by a nitrogen atom. m represents an integer of 3'' or 4.

On the other hand, suitable hardening agents having three or more active halogens include the following general formula Cll-4] and general formula (n-5)
A group of compounds represented by and the following general formula [''ll-6]
Among the compounds represented by the above, partial hydrolysates of compounds having three or more active logens can be mentioned. Further, as the hardening agent according to the present invention which is advantageously used in the invention, for example, US Pat. No. 3.057.723, US Pat.
Examples include polymeric hardeners described in Japanese Patent Nos. 396,029 and 4,161.407.

General formula Cm-4) In the formula, R3 and R1 are hydrogen atoms or alkyl groups, Y
is an alkylene group having 2 or more carbon atoms, a cyfuroa group (R,
represents a hydrogen atom or an alkyl group, m and R8 represent an integer of 2 or 3), or an atom or an alkyl group, m and n represent an integer of 2 or 3).

In the formula, X Rn, B"Q and RIO represent a hydrogen atom or an alkyl group, "m represents an integer of 2 or 3, and ns represents an integer of 1 or 2.

General formula [II-6] In the formula, a hydrogen atom or an organic residue, X' is (m, +
R4) valent organic residue (e.g. alkylene group, phenylene group), - represents O or a positive integer, R4 represents a positive integer,
−10n4≧2.

Hereinafter, typical examples of hardeners according to the present invention represented by the general formulas [:n-1:l to [ll-6:l] will be listed, but the invention is not limited thereto.

ll-1cH, ocoNHcoca=c Torimushi CHOCONHCOCH=CH.

CH,0CONHCOCH=CH.

n-4CI(,-C(CHtSO,C)I=CH,).

II-5Cm R5-C(CH2SOx cH==c
H,) sn -60aHtt-C (CHz 802 C
H=CHri! [-7CH, -CH5OICH2-CH-
80, CH=CH.

So, CH=CH.

n-8CH, =CH8O, CH2-CI(-CH2So
, CH=CH.

t So, CH=C bird ll-9CH.

圀CHs -CCHt CH-C(CHs)! -S
Ox CH"Ck5SOzCH"CHz 80
2CH=CHtCH, SO, CH=CH.

n-11So, CH=CH.

CH,=CH3O,0H2-C-C(CH,), OHS
o, CI (=C n-12So, CH=CH.

CH,=CH8O□CI(t-C-C(CHm)t
OCH=CH1(zOHso, ca=chorse II-13CH.

■ll-14(CH,=CH8O,CH,), C-CH,
So, CH, CH, SC bird Cool II-15 (CHx
=CH8O1CHJaCCHxSOICHtCHxNH
CH1COOHII-16(CH,=CH3O□CH,
), C-CH, So, CH, CH, NHCH, C-CH, So
, Hn-17(CHl-CH8O1CH180-CH,
So, CH, CI, OH[-18(CH,=C) ISO
,CH2)sC-CH,BrI[-19(CH,=CH
8O, CHI) AC-C Tori So, CH, CH, NHCH
,C00C,H.

n-20 (C horse = +C) to Is), CH-CH (So□
CH=CH2).

I[-2I C(CH, So, CH=CH,)4
II-220 is also ■-23CH, CM.

H-25(CH=CH100,), cH-CH-CH(
SO2CH=CHt)180, CH=CH.

n-27 (C horse: “CH30tCH*) sc-NO!!
l-28 (C = CH8O, CH, C-N) (.

[-29(CI(,=CH8O,CHl), CH30C
H*[-30(CH,=CH8O,CH,)AC-NH
CHlCOOHn-31(CH,=CH8O,CH,)
,C-NHCH,CH,SO,HI[-32(Chorse=C
H8OI CH2)A CCHt 0CHx C(CH
t SOI CH=CH1%1i-33CH,C(CH
, OCH, So, CH=CH,).

[-34C(CH,OCH,So,CH=CH,)4[
-35N (CH, CHlOCR, So, CH=C bird).

n-36(CH,=CH8O,CH,), CHCH(C
H, So, CH=C horse).

IF-37 (CH,=CH8O,CH,), CCH,O
CH,C(CH,5oICH=CH,)3II-42
CH.

(CH,=CH8O,CHCHICOOC horse)4C■-
43U(CH,=CH8O,CHCHICOOC)I,),C
-CH.

ll-45? H.

CH.

[-470H.

CH.

■ ”-49CH,CH.

II ■-52 ■-54 ■〼　　　　. H3 li 　 　 　 　 　 n-57CH.

■-Guo■-59 ■-ω ■-74 ■-75 ■-76 l-77 Among the hardeners that have fallen down above, those with poor solubility in water (
(found in some vinyl sulfone thread hardeners), reacts with the vinyl sulfone group (e.g., SR group,
groups, NH1 groups, etc.) and water-soluble groups (e.g., OH groups,
Water solubility can be imparted by reacting with a compound having (C0OH group, 5O3H group, So, FI group, O20, H group, or a salt thereof). One or more of these vinyl sulfone group-reactive groups and water-soluble groups may be contained in the molecular structure. The water-solubility imparting compounds preferably used in the present invention are listed below.

A-I H, NC00Na A-2H, NSO, K A-3H8CH, C00H A-4H8CH, COONC 00N H8CH, C00K A-6H8CH, C00Li A-7H3CI(, CH, C00H A-8H8CH1C Horse C00K A-12H2NOH, CH ,0H A-13H,NCR,Cl20SO,HA-14H,N
CH2CH1080,KA-15H,NCH,C00H A-16HtNCFItCOONa A-17CH,N)ICH,C00K A-18H,NCH,So,HA-19CH,NHCHlSo,K A-20H,NCH,CH,So,HA- 21H, NCH, CH, 80, K A -220) ImNHCHt CH2SO3NmA-
23HN (CH, C horse OR).

A-24HNCCHt 0%08OsK) *A-25
CH, NHCH, CH3OK, So, HA-27C1H
, NHC Tori CH1C Horse C Horse SO, UA-28Ct H
, NHCH, CHt CHt CHt 5O3NaA
-31HN(CH2C00H)z A-33 Nanbe CI (ICOOK)* A-34H8CH,CHCH,O)l OH A-35HOCHlCHCH,OH OH A-37Ct(3NHCH, COONa and the above hardener (hereinafter referred to as H) In order to react the water-solubility-imparting compound (hereinafter referred to as A), the solution of A may be added to the solution of H and kept at room temperature or heated. When using a group that is not specified as , the water-soluble group in the reaction product may be converted into a salt form by reacting with an alkali after the reaction.The reaction molar ratio of ■ and A is as follows: The number of groups varies depending on the number of reactive groups in A, but generally when reacting H having one vinylsulfonyl group with one having one reactive group, A 'i It is best to react in a molar ratio of 0.5~! In particular, A1~ for 81 moles.
1-2) When reacted in molar ratios, hardeners with desirable properties can be obtained. Further, the desired reaction amount varies depending on the type of reactive group of A, but for example, the reactive group is 18H.
In the case of a group or a =NH group, the above-mentioned reaction amount is desirable; however, in the case of a reactive group or a group, it is desirable to react in an amount of 3A. The reaction product obtained by the reaction between H and humans may be a single compound, but generally it is not possible to obtain a product consisting only of a single compound. That is, for example, some of the vinylsulfonyl groups of H are mainly annihilated by the reaction with the reactive M of A, and some unreacted H or all the vinylsulfonyl groups in the molecular structure become A. The reaction product is often obtained in the form of a mixture containing quenched by reaction with the reactive groups of. The effect as a good water-soluble hardening agent according to the present invention is obtained when some of the vinylsulfonyl groups of H are annihilated by reaction with the reactive group of A, especially when vinylsulfonyl groups are present in the molecular structure. It should be noted that even if a small amount of other reaction products such as those mentioned above are present, it does not have a negative effect on the operation and effect, although this is considered to be indicated by the fact that three or more remain. Therefore, the reaction product may be isolated as necessary, for example, by chromatography, but in actual use, it is necessary to isolate the reaction product as a mixture rather than isolating only the main part of the reaction product. It is preferable to use it as is.

The hardeners having three or more functional groups used in the present invention can be used alone or in combination.

Furthermore, in addition to the hardening agent of the present invention, a conventionally well-known bifunctional hardening agent can also be used in combination.

Examples of such hardening agents include ketone compounds such as diacetyl, dichlorobentanedione, bis(2-chloroethylamide, 2-hydroxy-4,6-di-chloro-
1,3,5-)Ryazine, U.S. Pat. No. 3,288.77
No. 5, No. 2.732.303, British Patent No. 974.
Compounds containing reactive halogens, divinyl sulfone, 5-7 cetyl-1,3-diacryloylhexahydro-1,3,5 as shown in the specifications of No. 723 and No. 1.167.207, etc. -Triazine, etc. U.S. Patent No. 3,635.718, U.S. Patent No. 3,232.763
No. 994,869, U.S. Patent No. 2.73
2.316, 2.586,168, 3.1
No. 03,437, No. 3,117,280, No. 2.
No. 983,611, No. 2.725.294, No. 2
．． No. 725°295, No. 3.100.704, No. 3,091.537, No. 3.321.313, No. 3.543,292, etc. compounds can be used.

The hydrophilic colloid substance used as a binder in the present invention is mainly gelatin, but partially modified gelatin and the like can also be used.

Furthermore, some of the gelatin may be replaced with albumin, agar, gum arabic, alginic acid, casein, partially hydrolyzed cellulose derivatives, polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, polyacrylic acid, polyacrylamide, imidized polyacrylamide, Polyvinylpyrrolidone and copolymers of these vinyl compounds can also be used.

An embodiment of the present invention in which a hardening agent having three or more functional groups in one molecule and gelatin are reacted in advance in an aqueous solution is as follows.

The gelatin used is not particularly limited, but the reaction proceeds more easily with high molecular weight and high viscosity gelatin than with low molecular weight and low viscosity gelatin. The reaction conditions are controlled by the reaction temperature, reaction time, concentration of gelatin aqueous solution, etc. depending on the type of gelatin. During the reaction, it is necessary to maintain the pH of the gelatin aqueous solution at a neutral to slightly acidic level; on the acidic side, the progress of the reaction is delayed, and on the basic side, with a pH of 13 or higher, thickening and gelation occur, and the functional group of Schiffly is As the hardening agent decreases, it loses its ability as a hardening agent.

Among general photographic gelatins, it is preferable to react at a gelatin aqueous solution concentration of about 12 to 20% for low viscosity gelatin, about 8 to 15% for medium viscosity gelatin, and about 6 to 12% for high viscosity gelatin. The reaction is carried out at 45 to 70°C over several minutes to several hours, but it is effective to carry out the reaction at around 65°C. The reaction can be terminated by lowering the temperature to below 40°C and diluting with water at the same time.

The amount of hardener used varies depending on the type of gelatin used in the reaction and the purpose of hardening, but is preferably about 0.5 to 10% (weight ratio) based on gelatin.

There is a method called seasoning as a method of accelerating the hardening of a gelatin film.

Generally, curing Me when curing gelatin etc. is dependent on humidity, and the lower the humidity, the slower the curing speed becomes. The hardening rate also depends on the temperature, and the higher the temperature, the faster the sanding rate.

Thereupon, the coated and dried photosensitive material is placed in a closed container, preferably in a plastic seal, and heated to a temperature of preferably 35 to 40°C.
Leave at 5°C for several days, preferably 3 to 6 days.

This method is called seasoning and is generally widely used as a method for accelerating the hardening of gelatin films.

A surfactant may be added to the photosensitive material of the invention alone or in combination. They are coating aids, emulsifying and dispersing agents, 1. It is applied for sensitization, improvement of photographic properties, antistatic, antiadhesion, etc. These surfactants include natural surfactants such as saponin, alkylene oxide threads, glycerin,
Nonionic surfactants such as glycidol thread, higher alkylamines, quaternary ammonium salts, pyridine, others (cationic surfactants such as DfX, phosphonium, or sulfonium, carboxylic acids, sulfonic acids, phosphoric acids, sulfuric acids) They are divided into anionic surfactants containing acidic groups such as esters and phosphates, and amphoteric surfactants such as sulfuric acid or phosphoric acid esters of amino acids, aminosulfonic acids, and amino alcohols.

No. 226, No. 2.739,891, No. 3.068
, No. 101, No. 3.158.484, No. 3,20
1.253, 3,210,191, 3,2
No. 94,540, No. 3,441.413, No. 3,
No. 442.654, No. 3,475.174, No. 3
．． No. 545.974, British Patent No. 1.077.317, British Patent No. 1,198,450, published in West Germany (
OLS) No. 1,942.665, etc.

Additionally, an organic fluorine-containing surfactant may be added.

The organic fluorine-containing surfactant that can be used in the present invention includes a chain or cyclic compound containing at least 3 fluorine atoms and at least 3 carbon atoms, and includes a cationic thread, a nonionic group,
Any type of anionic thread or betaine thread can be preferably used.

Typical organic fluorine-containing surfactants used in the present invention include, for example, U.S. Pat.
, No. 666.478, No. 3,754,924, No. 3,775.126, No. 3,850,640, British Patent No. 1.330.356, Japanese Patent Publication No. 1987-2
It is described in Publication No. 9691 and the like.

Particularly preferred organic fluorine-containing surfactants in the present invention are anionic organic fluorine-containing surfactants.

In the present invention, a matting agent can be used in the surface protective layer of the photosensitive material. The matting agents used are inorganic substances such as silica, magnesium oxide, titanium dioxide, calcium carbonate, etc., polymethyl methacrylate, cellulose acetate propionate, or JP-A-51-13595.
Organic substances such as alkali-soluble porous polymer particles made of acrylic acid and methyl acrylate as described in Publication No. Preferably, those having a diameter of 0.5 to 10μ are particularly preferable.

Further, the surface protective layer may contain various photographic additives including colloidal silica.

The light-sensitive material of the present invention has at least one silver halide emulsion layer and a protective layer supported on a support. For the prevention layer, filter layer, intermediate layer, undercoat layer, etc., known materials can be used.

The silver halide used in the silver halide emulsion layer of the light-sensitive material used in the present invention is generally one in which silver halide grains are dispersed in a hydrophilic colloid. Silver, silver iodine, silver chloride iodobromide,
These silver 10genides can be obtained by the ammonia method, neutral method, acid method, British Patent No. 635.841, U.S. Patent No. 3,6
It can be produced by various methods such as the so-called convergence method and simultaneous mixing method described in No. 22,318.

The above silver halide emulsions can also be chemically sensitized by conventional methods. Chemical sensitizers include, for example, as shown in U.S. Pat. No. 2,399,083, U.S. Pat. Gold compounds such as gold chloride and gold trichloride, U.S. Patent Nos. 2.445.060 and 2.54
No. 0.086, No. 2.566゜245, No. 2.5
No. 66,263, salts of noble metals such as platinum, baladicum, iridium, rhodium, ruthenium, as shown in U.S. Pat. No. 2,598,079, U.S. Pat.
No. 74.944, No. 2.410.689, No. 3,
Sulfur compounds that react with silver salts to form silver sulfide as described in U.S. Pat. No. 189.458, U.S. Pat. .518,698, 2,521.925, 2.521.926, 2.694.637,
Examples include stannous salts, amines, and other reducing substances as described in Patent Nos. 2.983,610 and 3.201.254.

Furthermore, these silver halide photographic emulsions can be subjected to spectral sensitization or superchromatic sensitization, if necessary, by using cyanine dyes such as cyanine, merocyanine, and carbocyanine alone or in combination, or in combination with styryl dyes, etc. It can be performed. These color sensitization techniques have been known for a long time and are described in U.S. Patent Nos. 2.688.545 and 2.9.
No. 12.329, No. 3,397゜060, No. 3,
615.635, British Patent No. 3,628,964, British Patent No. 1,195.302, British Patent No. 1,242.588, British Patent No. 1,293°862, West German Patent Application No.
LS) No. 2,103,326, No. 2.121.7
No. 8Cl, Special Publication No. 43-4936, No. 44-1403
There is also a description in Publication No. 0, etc. The selection can be arbitrarily determined depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the photosensitive material.

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.

Those compounds are 4-hydroxy-6-methyl-1,3
, 3a, 7-titrazaindene, 3-methylbenzothiazole, 1-phenyl-5-mercaftotetrazole, many heterocyclic compounds, mercury-containing compounds, mercapto compounds, metal salts, and many other compounds have been known for a long time. There is.

In the present invention, examples of the support on which the non-photosensitive hydrophilic colloid layer, silver halide emulsion layer, and other auxiliary layers according to the present invention are coated include sululose nitrate, cellulose ester film such as cellulose acetate, and polyethylene terephthalate. Polyester films such as
Polyvinyl acetal film, polyvinyl chloride film, polystyrene film, polycarbonate film, baryta paper, polyethylene-coated paper, etc. are preferably used.

The selection of coating methods for the constituent layers of other photosensitive materials is important in order to ensure uniform quality and productivity.

For example, it can be selected from Ekhateinov coating, double-roll coating, curtain coating, etc. Among them, two or more types can be used, but from the viewpoint of productivity, a speed of 30 m /rnx or more is preferable.

In addition, for substances such as hardeners, which have quick reactivity and will cause gelation before coating if added to the coating solution in advance, it is recommended to mix them using a static mixer or the like immediately before coating. is preferred.

The photosensitive material according to the present invention may be used for general black and white use, X-ray use, printing use, micro use, electron beam recording use, infrared ray photosensitive material use, color use, etc. It is suitable for color photosensitive materials that require high film thickness.

After exposure, the photosensitive material of the present invention can be used for general black and white use, micro use,
An image can be obtained by a developing method that is normally used for photosensitive materials for photosensitive materials, for photosensitive materials, and for color photosensitive materials, depending on the purpose.

The basic steps of photographic processing are development and fixing, and further treatments such as hardening, stopping, bleaching, and stabilization can be added as necessary.

The developer used for development is an ordinary black and white developer, and this developer contains developing agents such as hydroquinone, aminophenol, phenidone, etc., as well as hydroxide (IJium, sodium carbonate, etc. if necessary). It may contain alkaline agents such as, preservatives such as sodium sulfite, pH buffering agents, development accelerators, development inhibitors, surfactants, and the like.

The fixing solution used for fixing contains a silver halide solvent such as thiosulfate, ammonium thiosulfate, and ammonium thiosulfate, and may further contain various additives as necessary. Specifically regarding the processing of color photosensitive materials, the basic processing steps in the negative-positive method include color development, bleaching, and fixing steps. The basic processing steps in the reversal method are development with a black and white negative developer, followed by white exposure or treatment with a bath containing a fogging agent, followed by color development, bleaching and fixing. These basic processing steps may be performed independently, but instead of performing two or more processing steps, a single processing may be performed using a processing liquid that has these functions. For example, a one-bath color processing method containing an ethylenediaminetetraacetate iron GID complex salt bleaching component and a thiosulfate fixing component may be used.

There are no particular restrictions on the processing method for color photosensitive materials.
Any processing method can be applied. For example, representative methods include the method of performing color development, bleach-fixing, and further washing with water and stabilizing treatment if necessary, as described in U.S. Pat. No. 3,582.322; After color development as described in the specification of No. 910,002, bleaching and constant M1 separation are performed, and if necessary, further washing with water,
Method of stabilizing; or US Pat. No. 3,582.
As described in No. 347, pre-hardening, neutralization, color development, stop fixing, water washing, bleaching, fixing, water washing, post-hardening,
A method in which washing is carried out in the order of water; a method in which the steps are carried out in the order of color development, washing with water, supplementary color development, stopping, bleaching, fixing, washing with water, and stabilization as described in JP-A-50-54330; US Patent No. 3, Prehardening, neutralization, water washing, first development, stopping, water washing, color development, as described in No. 307,263;
A method of stopping, washing with water, bleaching, fixing, and washing with water in this order; as described in JP-A-50-36126,
Neutralization, first development, stop, water washing, color development, stop, water washing,
A method in which bleaching, organic acid bath, fixing, and water washing are performed in this order; JP-A-5
0-81538, first development,
Non-fixing silver dye bleach, washing with water, color development, rinsing with acid, washing with water, bleaching, washing with water, fixing, washing with water, stabilization, washing with water in the order; US Patent No. 2.623,822, US Pat. No. 2.814 , 565, in which the developed silver produced by color development is halogenated and bleached, and then color development is performed again to increase the amount of dye produced; or U.S. Pat. No. 3,674,990 ,
No. 3,761.265 Mei A1 Tani, West German Application Publication (O
LS) No. 2,056,360, JP-A-47-633
No. 8, No. 47-10538, West German Publication (OLS)
) No. 2,226.770, JP-A-48-9728,
Processing may be performed using any method such as the method of processing a low silver content light-sensitive material using a peroxide or a cobalt complex salt as described in Dowa No. 9729, etc. In addition, these treatments may be carried out at high temperatures of 30°C or higher in order to perform them quickly, or may be carried out at room temperature or below 30°C in special cases. Line 9..) KA8 Yes H
'a,. A series of tanks. Process. The constant temperatures may be the same or different.

Typical color developing agents include P-phinidiamine diamine threads and aminophenol-based ones, and the following are preferred examples.

4-Amino-N, N-diethylaniline, 3-methyl-
4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3
-Methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-β-methanesulfonamidoethyl-4-amino-NIN-diethylaniline, 3-methoxyethylamino-N-ethyl-N-β -Hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-
N-β-methoxyethylaniline, 3-acetamide-
4-amino-N, N-diethylaniline, 4-amino-
N, N-dimethylaniline, N-ethyl-N-β-[β
-(β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline, N-ethyl-N-β-(β
-methoxyethoxy)ethyl-3-methyl-4-aminoaniline and salts thereof, such as sulfate, hydrochloride, sulfite, and P-toluenesulfonate. Further, JP-A-48-64932, JP-A-50-131527, JP-A-50-17246, and the Journal of the American Chemical Society (J.
our own of American Chemistry
al 5ociety) Volume 73, 3100-3
Compounds described on page 125 (1951) can also be used.

Moreover, various additives can be added to the color developing solution as necessary. The main examples include alkaline agents (e.g. alkali metal and ammonium hydroxides, carbonates,
Phosphates), pH regulators or buffers (e.g., weak acids and bases such as acetic acid and boric acid, and their salts), development accelerators (e.g., U.S. Pat. Nos. 2,648,604 and 3).
, various pyridinium compounds and cationic compounds described in , 571.247, etc., potassium nitrate and sodium nitrate, U.S. Patent No. 2.533,990,
Polyethylene glycol condensates and their derivatives as described in Patent No. 2.577.127, Patent No. 2.950.97Q, etc., British Patent No. 1,020,03
2, nonionic compounds such as polythioethers as described in US Patent No. 1.020,033, and sulfides as described in US Patent No. 3,068,097 ester-containing polymer compounds, other pyridine, ethanolamines, organic amines, benzyl alcohol, hydrazine, etc.), anti-capri agents (e.g. alkali bromide, alkali iodide, U.S. Pat. No. 2.496.940, Including the nitrobenzimidazoles described in Specification No. 2,656,271,
Mercaptobenzimidazole, 5-methylbenzotriazole, 1-phenyl-5-mercaptotetrazole, U.S. Pat. No. 3,113,864, U.S. Pat. No. 3.342.
No. 595, No. 3,295゜976, No. 3,615
．． No. 522, compounds for rapid processing liquids described in the specification of No. 3.597.19999, nitrobenzoic acid described in JP-A-49-106832, JP-A-50-13711
Benzothiazolium derivatives as described in Publication No. 36 or phenazine-N-oxides as described in Japanese Patent Publication No. 46-41675 and others 1 Scientific Photographic Handbook 1
anti-capri agents as described in Vol.
No. 1,144,481, No. 1.251.55
No. 8, the stain or sludge preventive agent, as well as the interlayer effect accelerator and preservative (e.g. sulfite, acid sulfite, hydroxylamine) described in U.S. Pat. No. 3,536,487 etc. hydrochloride, formaldehyde pisulfite, alkanolamine sulfide adduct, etc.).

When the present invention is applied to a color photosensitive material, a bleaching treatment is carried out by a conventional method after the color development treatment. This process may be performed simultaneously with fixing or separately. This processing solution can also be used as a bleach-fixing bath by adding a fixing agent if necessary.

Various compounds are used as bleaching agents, among which red blood salt, dichromate, iron (IID aminopolycarboxylic acid, aliphatic polycarboxylic acid metal salt, persulfate, British Patent No. 774.194) , No. 1,032,024, No. 949,440, copper complex salts as described in Belgian Patent No. 717,139, West German Patent No. 93
Cobalt complex salts as described in British Patent No. 777.635, Japanese Patent Publication No. 41-110
Iodine as described in Publication No. 68, Special Publication No. 41-
Salad powder and sulfamine as described in US Pat. No. 11068, US Pat.
．． 529.981, quinones as described in U.S. Pat. No. 2.748.000, U.S. Pat.
5.477 and 2.705.201, such as P-sulfophenylquinones and nitrone compounds, used alone or in appropriate combinations.

Additionally, bleach or bleach-fix solutions are described in U.S. Patent No. 3.042.
．． It is also possible to add various additives, including the bleaching accelerators described in Japanese Patent Publications No. 520, No. 3,241,966, Japanese Patent Publications No. 45-8506, and Japanese Patent Publication No. 45-8336.

〔Example〕

EXAMPLES The present invention will be described in more detail with reference to Examples below, but the embodiments of the present invention are not limited thereto.

Example 1 A blue-sensitive emulsion layer and a protective layer having the compositions shown below were simultaneously coated in a multilayer manner on top of cellulose triacetate paste using a slide hopper method to prepare eight types of samples (A-I()).

Layer 1: Blue-sensitive emulsion layer Silver iodobromide emulsion (containing 7.5 mol% silver iodide)'f! : Chemically sensitized with gold and sulfur sensitizer, 4-hydroxy-6-
Methyl-1,3,3m, 7-tetrazaindene 1. O
A blue-sensitive silver halide emulsion was prepared by adding I and preparing in a conventional manner.

Further, per mole of silver halide, in addition to yellow coupler (Y-1) of the following structural formula (200 II), 200.9 dibutyl 7-thale and 600 m' of ethyl acetate, sodium triisopropylnaphthalene sulfonate was dissolved by heating. After adding it to a gelatin solution and emulsifying and dispersing it in a colloid mill, the fine oil droplet dispersion from which ethyl acetate had been removed was added to the above emulsion, and a blue-sensitive halogen was added.

A silver oxide coating solution was prepared and coated to give a dry film thickness of 4.8 μm.

Layer 2: Protective layer: 41 g of gelatin and a hardening agent and a slip agent as shown in Table 1-1 were added per 100 d of the coating solution, and the dry film thickness was 1.
．． It was applied to a thickness of 1μ. The amount of gelatin at this time is L51/g.

A slippery agent dispersion was prepared as follows.

Solution C 7% gelatin aqueous solution 5o Go solution A and B solution ti
The mixture was combined and emulsified using a pulp homogenizer manufactured by Manton-Gaulin with a tongue force of 250 yu/min to obtain an O/W type fractional dispersion. At this time, the particle size of the dispersion in the gelatin aqueous solution was controlled to be 0.8 μm. Solution C was added to the obtained dispersion, and water was added to give a final slip agent dispersion of 8011 Ll.

Table 1-1 Hata Pretreatment here refers to a 10% aqueous solution of medium viscosity gelatin mixed with a hardening agent at pH 6.2 to 6.5 and ω to 5°C. Refers to the means of the present invention in which a portion of the hardener functional group is reacted with the gelatin.

For each sample thus obtained, the coefficient of friction and the minimum back profile at which scratches occur were measured. The coefficient of friction was measured according to the American ASTM method, D-1814, and was expressed as a coefficient of kinetic friction against light-shielding paper for photographic film. The load at which scratches occurred was measured by continuously applying a load to a needle with a diameter of 0.1 lubricant and scratching the surface of the film, and measuring the minimum load at which scratches occurred.

In addition, some of these sample pieces were placed in close contact with a transparent rectangular wave chart and exposed to blue light, and some of them were exposed to blue light through a wedge, and then processed through the processing steps described below. Tometry evaluation, sharpness and turbidity were measured.

The results are shown in Table 1-2.

Processing process (38℃) Processing time Color development...
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・3 minutes 15 seconds bleaching・・
・・・－・・・・・・・・・・・・・・・・・・ Song・・・・・・Song 6 minutes 30 seconds Washing・・・・・・・・・
......Song...Song...Song...3
Fixation for minutes and 15 seconds... Song... 4... Song... 6 minutes and seconds Washing... Song...
・・・・・・・・・Song・・For song・・Song 3 minutes 15 seconds Stable bath・・・・・・・・Song・・Song・・Song・・For song・The composition of the treatment liquid used in each 1 minute (t) second treatment step is as follows.

Color developing solution composition: Bleaching solution composition: Fixing solution composition: Stabilizing bath composition: Table 1-2 As is clear from the table, Samples G and H according to the present invention showed further smoothness without deteriorating photographic sensitivity and sharpness. It is possible to improve performance. Addition of slip agent (sample C)
and D) significantly impair sharpness and increase the amount of hardener (
Samples E and F) are clearly accompanied by deterioration in photographic performance, such as a decrease in sensitivity due to slow hardening. According to the invention,
The anti-slip agent is more effective than expected without any deterioration in photographic performance.

Example 2 On a transparent support consisting of a subbed cellulose triacetate film and having an antihalation layer (containing 0.40 I black colloidal silver and 3.0 gi gelatin),
Eight samples (graves 1 to 8) were prepared by sequentially applying the following layers. In all of the following examples, the amount added to the light-sensitive material is shown per 1 m, and the amounts of silver halide emulsion and colloidal silver are shown in terms of silver.

Layer 1: Low-sensitivity red-sensitive emulsion layer A low-sensitivity red-sensitive silver iodobromide (containing 7 mol % silver iodide) emulsion of 1,41 color-sensitized to red sensitivity and 1.2II of gelatin and 0.81 of 1-Hydroxy-4-(β-methoxyethylaminocarbonylmethoxy)-N-[δ-(
2,4-di-t-amylphenoxy)butyl-2-naphthamide [hereinafter referred to as cyan coupler (C-1)],
0.075.9 of 1-hydroxy-4-(4-(1-hydroxy-δ-acetamido-3,6-disulfo-2-
naphthylazo)phenoxy)-N-[δ-(2,4-di-t-amylphenoxy)butyl-2-naphthamide.
disodium [hereinafter referred to as colored cyan coupler (CC-
1)] and o, ois II of 1-hydroxy-2-(J-(2,4-di-t-amylphenoxy)-
n-butyl]naphthamide, 0.07 JF of 4-octadecylsuccinimine)"-2-(1-phenyl-5-tetrazolylthio)-1-indanone [hereinafter referred to as DIR compound (D-1)] was dissolved. A low-speed red-sensitive emulsion layer (hereinafter referred to as RL) containing 0.65 J of tricresyl phosphate (TCP).

Layer 2: High sensitivity red-sensitive emulsion layer 1.3! High-sensitivity red-sensitive silver iodobromide (containing 6 mol % silver iodide) emulsion of i, 1. High sensitivity containing 0.23.9 TCP dissolved in i gelatin and 0.21 g nail cyan coupler (C-1) & 0.02 J colored cyan coupler (CC-1) red-sensitive emulsion layer (hereinafter referred to as RH). □ Layer 3: Intermediate layer 0.07 N of 2.5-di-t-octylhydroquinone [hereinafter referred to as antifouling agent (Hq-x)] dissolved in 0.04.9 n-dibutyl 7-thalerate ( DBP) and an intermediate layer (hereinafter referred to as IL) containing gelatin of o, a Ij.

Layer 4: Low-speed recording emulsion layer color sensitized to green sensitivity 0,80! low sensitivity silver iodobromide (containing 6 mol% silver iodide) emulsion of i and gelatin of 2.2.9 and 1-(2,4,6-dolichloro7enyl)-3 of 0.8.9 -[:3-(2,4-di-t-amylphenoxyacetamide)benzamide]-5-pyrazolone [hereinafter referred to as magenta coupler CM-1], 0.1
5.9 1-(2,4,6-)lichlorophenyl)-4
-(1-naphthylazo)-3-(2-chloro-5-octadecenylsuccinimidoanilino)-5-pyrazolone [hereinafter referred to as colored magenta coupler (CM-1)], 0.016F DIR compound ( D-1) dissolved in 0,95,! A low-sensitivity green-sensitive emulsion layer (hereinafter referred to as GL) containing TCP of i'.

Layer 5: High-sensitivity recording emulsion layer 1,81 high-sensitivity green-sensitive silver iodide (containing 6 mol % silver iodide) emulsion sensitized to green sensitivity, 1.9 g of gelatin and 0.20. 9 of the magenta coupler CM-1) and 0.041 of the colored magenta coupler (CM-1) dissolved in the TCP'i of 0.25>

Layer 6: Yellow filter layer 0.15.9 of yellow colloidal silver, 0.11 g of DBP dissolved in 0.2& of antifouling agent (HQ-1) and 1.
One layer of yellow filter (hereinafter referred to as YC) containing 5I gelatin.

Layer 7 - Low-speed blue-sensitive emulsion layer Low-speed silver iodobromide (containing 4 mol % silver iodide) emulsion of 0, 21 color-sensitized to blue sensitivity and gelatin of 1.91 and Examples of 1.1 Yellow coupler used in 1 (Y-1
BL).

Layer 8: High-speed blue-sensitive emulsion layer 1, OI, color sensitized to blue sensitivity! High-sensitivity silver iodobromide emulsion (containing 2 mol% silver iodide), 1.5 g' of gelatin and 1.30 g of yellow coupler (Y-1) dissolved in 0.65.9 TCP'. A high-speed blue-sensitive emulsion layer (hereinafter referred to as BH).

Layer 9: Protective layer A protective layer containing 2.3 g of gelatin and the slipping agent and hardening agent shown in Table 2-1 (hereinafter referred to as PR).

On the other hand, samples (&9 to 16) having the same protective layers as Samples 1 to 8 were also produced, except that the layer groove composition was as follows.

Samples 9 to 160 Layers Constituent Layers -1 Same layer as above RL -2 Same layer as above IL -3 Same layer as above GL -4 Same layer as above IL -5 Same layer as above BL -6 Same layer as above fL - 7 Same layer for the RH - 8 Same M for the IL - 9 Same layer for the GH - 10 Same layer for the IL - 11 Same layer for the BE - 12 Same for the PR Below Gold Eye / Snake / Each obtained in this way The minimum load at which an abrasion occurs on the sample was measured. That is, the needle head diameter is 0. Color development (fog) after the surface of the film was scratched by continuously applying a load to the h+m needle and treated in the same process as in Example 1.
Measure and mourn the minimum load that occurred.

On the other hand, some of these sample pieces were brought into close contact with a transparent rectangular wave chart to give white exposure, and some of them were passed through a wedge to give white exposure, and then treated with the same processing steps as in Example 1 to obtain the resulting pigment. About the image (sensitome) IJ-
Evaluation and sharpness t-measure measurements were made.

Table 2-2 Table 2-3 As is clear from the table, Samples 5, 6° 7 and 8 according to the present invention are superior in scratch resistance, and are also excellent in high sensitivity and sharpness. In addition, 1 high-sensitivity layer snow as in samples 9 to 16,
In a layer structure in which the snow image sensitive layer-unit is located far from the support, the effect is more pronounced.

〔Effect of the invention〕

As is clear from the examples, by providing the protective layer of the present invention, it is possible to form images with excellent image quality, especially sharpness, without causing the sweating phenomenon caused by the slippering agent, and moreover, it is possible to form images with excellent image quality and sharpness. Even after being stored under humid conditions, the inconvenience of various oil-based additives, etc., which deteriorates the photographic and w properties is eliminated. Furthermore, overhardening, which tends to occur in photosensitive materials with a large number of layers, was hardly observed, the photosensitive material maintained high sensitivity, and its scratch resistance was significantly improved.

Claims (3)

[Claims] (1) In the protective layer of a photographic light-sensitive material having at least one silver halide emulsion layer on a support, (a) a slipping agent, and (b) a hardening agent having three or more functional groups in one molecule. and gelatin reacted in advance in an aqueous solution state,
A silver halide photographic material characterized by containing. (2) The above-mentioned slipping agent has the following general formula [I-1], [I-
2], [I-3] and [I-4]. General formula [I-1] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, R_1, R_2 and R_3 each have 1 carbon number
Represents 0 to 20 alkyl groups. General formula [I-2] ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R_4 represents an alkyl group having 10 to 24 carbon atoms. m represents an integer from 2 to 4. Each R_4 may be the same or different. General formula [I-3] R_3COOR_6 In the formula, R_5 and R_6 each have 10 to 20 carbon atoms.
represents an alkyl group. The alkyl groups in general formulas [I-1], [I-2] and [I-3] may be linear or branched. General formula [I-4] ▲ Numerical formulas, chemical formulas, tables, etc. are included▼ In the formula, R_7 represents an aliphatic group or aryl group, R_8 represents a hydrogen atom or an alkyl group, and R_9 represents an alkyl group or an alkoxyalkyl group. A represents an aliphatic divalent residue. n is 0 or an integer from 1 to 12, p is 0-50, q is 2-50, x is 0-100, y is 1-50, z is 0-1
represents the number 00, and x+y+z is a number from 5 to 250. (3) The hardener has the following general formula [II-1], [II-2]
, [II-3], [II-4], [II-5] and [II-6]
] The silver halide photographic light-sensitive material according to claims 1 and 2, characterized in that it is selected from the compounds represented by the following. General formula [II-1] R(COCH=CH_2)_n formula,
R represents an n-valent organic residue, and n represents an integer of 3 or more. General formula [II-2]X(SO_2CH=CH_2)_n_
'In the formula, x represents an n'-valent organic residue, and n' represents an integer of 3 or more. General formula [II-3] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, one of R_1 and R_2 represents hydrogen, and the other represents hydrogen or a methyl group. A may be the same or different and represent a divalent bonding group or a single bond. B represents an m-valent aliphatic residue, an aromatic residue, or a saturated heterocyclic group which may be interrupted by a nitrogen atom. m represents an integer of 3 or 4. General formula [II-4] ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼ In the formula, R_3 and R_4 are hydrogen atoms or alkyl groups, Y is an alkylene group with 2 or more carbon atoms, a cycloalkylene group, a phenylene group, a biphenylene group , phenyleneoxyphenylene group, ▲Mathematical formulas, chemical formulas, tables, etc.▼
Group (R_3 is a hydrogen atom or an alkyl group, m_1 and n_1 are integers of 2 or 3) or ▲ Numerical formula, chemical formula, table, etc. ▼ Group (R_5 and R_7 are a hydrogen atom or an alkyl group, m_2 and n_2 are 2 or an integer of 3). General formula [II-5] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_5, R_9 and R_1_0 are hydrogen atoms or alkyl groups, m_3 is an integer of 2 or 3, and n_3 is 1
or represents an integer of 2. General formula [II-6] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1_1 is a hydrogen atom or an organic residue, and X' is (
m_4+n_4) valent organic residue, m_4 represents 0 or a positive integer, n_4 represents a positive integer, and m_4+n_4≧2.