JPH07319111A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the photosensitive material not deteriorated in resistance to stickiness and tackiness on the surface of a photograph even in running state after development processing in the case of reducing a binder amount. CONSTITUTION:The photosensitive material contains the fluorine-containing surfactant and the,binder in the total amounts of >=7.5g/m<2> and the fluorine atc>ms present on the uppermost surface of the photosejnsitive material on the image-forming side before development processing remains oh the surface after the development processing in an amount >=50% of the total fluorine atoms.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material for direct viewing which has suitability for rapid processing, and particularly to a silver halide photographic light-sensitive material excellent in surface quality of finished photographs even if the amount of binder is reduced. .

[0002]

2. Description of the Related Art Generally, a direct-viewing silver halide photographic light-sensitive material is subjected to development processing through processing steps of development, bleach-fixing and stabilization (or washing with water). In recent years, there has been an increasing demand for rapid processing, and the time required for this processing step is becoming shorter and shorter. For rapid processing, it is necessary not only to simply shorten the processing time but also to guarantee the quality of the photograph after the development processing.

In order to achieve rapid processing, from the silver halide photographic light-sensitive material side, the solubility of the silver halide emulsion is improved, the developability of the silver halide emulsion is improved, and the color developability of the colorant is improved. Means such as adjusting the hardness of the light-sensitive material may be used. However, there is a limit to the rapid processing that can be achieved while guaranteeing the photographic quality by only these means.

It can be easily guessed in the art that thinning the constituent layers of the silver halide photographic light-sensitive material is effective in addition to the above-mentioned means in order to achieve further rapid processing. The most effective means for thinning the constituent layers is to reduce the amount of binder. However, the binder exists as a dispersion medium for photographic emulsions (silver halide emulsions), photographic materials (colorants, dye image stabilizers, UV absorbers, etc.), so if the amount of the binder is simply reduced, the binder Since the ratio of each photographic emulsion and photographic material to the relative increase relative to each other, various harmful effects occur. As one of them, the stickiness of the photographic surface and the sticking resistance deteriorate, especially under high humidity,
Remarkable when handling photographs at high temperatures. This may deteriorate the handleability of the photographs and cause problems such as sticking to each other when left in a stacked state, easy fingerprints on the surface, and sticky feeling on the surface. Further, if the amount of photographic emulsion or photographic material is reduced along with the reduction of the amount of binder, generally the photographic performance is greatly changed, and the image quality as a photograph cannot be maintained.

Means for improving the sticky feeling and sticking resistance of the photographic surface are disclosed in JP-A-62-287238 and JP-A-1-228238.
Technology using the fluorine-based surfactant described in No. 60436,
There are techniques using the organopolysiloxane described in JP-A Nos. 50-117414 and 62-203152.

[0006]

Even when the above-mentioned technique is applied to a light-sensitive material having a reduced amount of binder, the stickiness and sticking resistance of the surface are improved. However, if the amount of binder is reduced, there is no problem if the process of developing the photosensitive material is in an extremely clean state (fresh state), but the state where the developing process is continuously performed and the process is in a fatigued state (running state). It was found that the surface characteristics of the photograph after the treatment deteriorated.

The present invention has been made in view of the above circumstances, and an object thereof is to prevent deterioration in stickiness and sticking resistance of a photographic surface after development in a silver halide photographic light-sensitive material having a reduced amount of binder. In particular, it is to provide a silver halide photographic light-sensitive material that does not deteriorate even when subjected to running processing.

[0008]

The above objects of the present invention include a fluorine-containing surfactant and a total binder amount of 7.5 g / m 2.
This is achieved by the silver halide photographic light-sensitive material having a ratio of ² or less and 50% or more of the fluorine atoms present on the extreme surface on the image forming surface side before the development treatment remains on the surface after the development treatment.

That is, the inventors of the present invention focused on fluorine, which is a fluorine-containing surfactant oriented on the extreme surface on the image forming surface side before and after the development processing, and the larger the reduction rate, the more the surface characteristics. The inventors of the present invention have found that the degree of deterioration is large and have reached the present invention.

The present invention will be described in detail below.

Generally, a surfactant is used in the light-sensitive material, but the surfactant present in the light-sensitive material has a surface orientation which is a characteristic of the light-sensitive material. Try to orient to the surface. Therefore, the surface active agent is selectively present on the surface of the light-sensitive material. Above all, the fluorine-based surface active agent has a large surface orientation, and therefore its properties are remarkable.

Further, the direct admiration light-sensitive material becomes an ornamental photograph through a developing process. Generally, in a development process, when a photosensitive material passes through each processing solution for development, bleach-fixing and stabilization (or washing with water), each photographic material, binder, etc. contained in the photosensitive material is processed. It elutes in. Surfactants also elute without omission, for example, and they are rather easy to elute. However, residual fluorine is still oriented on the surface of the photosensitive material after the development processing. Generally, the amount of surfactant present on the surface of the photographic material after the development processing is reduced with respect to the amount of surfactant present on the surface of the light-sensitive material before the development processing.

According to the present invention, 50% or more of fluorine atoms remain on the surface of the silver halide photographic light-sensitive material before development, which is present on the extreme surface of the image-forming surface, after development. Characterize. The residual fluorine atom content is preferably 60% or more, more preferably 70% or more, still more preferably 80% or more.

The ratio of fluorine atoms existing on the surface of the image forming surface before and after the development treatment in the present invention can be quantified by the ratio of the existence probability of fluorine atoms to all the atoms existing on the surface. The presence of atoms on the surface is recognized as the presence of atoms forming the extreme surface portion of the outermost surface layer, and the average abundance ratio of the atoms can be measured using an XPS surface analyzer.

Next, the method will be described.

The XPS surface analyzer is set under the following conditions. X-ray anode; Mg resolution: 1.5 to 1.7 eV (resolution is defined by the half-width of clean Ag3d5 / 2 peak) There is no particular limitation on the XPS surface analyzer, and any model can be used. In the invention,
ESCALAB-200R manufactured by VG was used.

Narrow scan is performed in the following measuring range,
The spectrum of each element was measured. At this time, the data acquisition interval is set to 0.2 eV, and it is necessary to integrate until the target peak has a count equal to or more than the minimum count number shown below.

Peak measurement range Minimum detection intensity (binding energy eV) (count) C1s 305 to 280 Arbitrary Fe2p3 / 2 730 to 700 600,000 Na (KL ₂₃ L ₂₃ ) 280 to 250 600,000 Auger peak For the obtained spectrum The peak position of C1s is 284.6.
Correct the energy position so that it becomes eV.

Next, COMMON DATA P made by VAMAS-SCA-JAPAN
In order to perform processing on ROCESSING SYSTEM Ver.2.3 (hereinafter referred to as VAMAS software), the above spectrum is transferred to a computer capable of using VAMAS software by using software provided by each device manufacturer. Then, using VAMAS software, the transferred spectrum is VA
After converting to the MAS format, data processing is performed.

Before starting the quantitative treatment, Co
The unt Scale is calibrated and the 5-point smoothing process is performed. The peak area intensity within the quantitative range shown in the following table, centered on the peak position of each element
Calculate (cps * eV). Using the sensitivity coefficients shown below, determine the atomic% of each element. The number of atoms is converted into the number of atoms with respect to 100 Fe atoms and used as a quantitative value.

Element Peak position (BE: eV) Quantitative range (BE: eV) Sensitivity coefficient F High BE side 6eV, Low BE side 6eV 4.26 Fe 719.8 vicinity High BE side 5eV, Low BE side 7eV 10.54 Na 264.0 vicinity High BE side Minimum value near 2 eV 7.99 Low BE side 6 eV Elements other than the above can be measured under the following conditions as necessary.

[0022]

[Table 1]

Due to the surface orientation described above, a fluorine-based surfactant is added to at least one constituent layer on the image forming surface side of the silver halide photographic light-sensitive material, whereby a fluorine atom is added to the surface on the image forming surface side. Can exist. The "residual ratio of fluorine atoms in the system with a reduced amount of binder" of the present invention can be obtained by using the fluorine-containing surfactant specified below.

In the general formula (FA) (Cf)-(Y) _n , Cf is an n-valent group containing at least 3 fluorine atoms and at least 2 carbon atoms, and Y is -COOM,-.
SO ₃ M, represents an -OSO ₃ M or -P (= O) (OM) 2. M represents a hydrogen atom or a cation such as an alkali metal or a quaternary ammonium salt, and n is 1 or 2.

The surfactant represented by the above general formula is hereinafter also referred to as "fluorine-containing anionic surfactant".

The more preferably used fluorine-containing anionic surfactant is represented by the following general formula (FA ').

General formula (FA ') Rf- (D) _t -Y In the formula, Rf represents a fluorine-substituted alkyl group or aryl group having 3 to 30 carbon atoms, and D is -O-, -COO-,-. CON
(R ₁₎ - or -SO ₂ N (R ₁₎ - represents a composed combine at least one divalent group having 1 to 12 carbon atoms. R ₁ represents an alkyl group having 1 to 5 carbon atoms, t is 1 or 2, Y is -COOM -, - SO ₃ M, an -OSO ₃ M or -P (= O) (OM) 2 Represents
M represents a hydrogen atom or a cation such as an alkali metal or a quaternary ammonium salt.

Specific examples of the compound represented by formula (FA) are shown below, but the invention is not limited thereto.

[0029]

[Chemical 1]

[0030]

[Chemical 2]

[0031]

[Chemical 3]

[0032]

[Chemical 4]

[0033]

[Chemical 5]

Particularly preferably, a surfactant containing at least one bond of --SO ₂ N (R ₁ )-and the following general formula (F)
The use of a surfactant represented by AS).

[0035]

[Chemical 6]

In the formula, R ₁ is a hydrogen atom or a carbon atom of 1 to
5 represents an alkyl group. B represents a divalent linking group. _{Examples, - (CH 2) p -} , - (CH 2) p -O- (CH 2) r -, - (CH 2)
_p − (CH ₂ CH ₂ O) _q − (CH ₂ ) _r , − (CH ₂ ) _p − (CHOH) _s − (CH ₂ )
_{r -, - (CH 2 CHOH} ) t - (CH 2 O) u - , and the like. However, p, r, t, u are 0-8, q, s are 1-20
Represents D represents COOM or SO ₃ M. M represents an alkali metal or a quaternary ammonium salt. x is 3-20, y is 0-10
Represents

As the surfactant represented by the general formula (FA-S), there are the followings in addition to those mentioned above.
It is not limited to this.

[0038]

[Chemical 7]

[0039]

[Chemical 8]

[0040]

[Chemical 9]

Further, in the present invention, the fluorine-containing surfactant used for obtaining the residual ratio of fluorine is represented by the following general formula (F
There is also a compound represented by K) (also called a fluorine-containing cationic surfactant).

General formula (FK) Rf'-L-X ⁺ Z ^{-In the} formula, Rf 'represents a hydrocarbon group having 1 to 20 carbon atoms, and at least one hydrogen atom is substituted with a fluorine atom.
L represents a chemical bond or a divalent group. X ⁺ is a cation,
Z ⁻ represents a counter anion.

As an example of Rf ', -C _k F _{k + 1} (k = 1 to 2
0, particularly preferably 3 to 12), -C _m F _2m , -C _m F _2m-1 (m =
2-20, especially 3-12 are preferable).

As an example of L, --SO ₂ N (R ₂ ) (CH ₂ ) _p- , --C
ON (R ₂ ) (CH ₂ ) _p −, − SO ₂ N (R ₂ ) (CH ₂ ) _p −, −CON (R ₂ ) (CH ₂ ) _p
−, − O (CH ₂ ) _p −, − (CH ₂ ) _p −, − O (CH ₂ CH ₂ O) _q (CH ₂ ) _p −, −
_{O (CH 2) p -,} - N (R 2) (CH 2) p -, - SO 2 N (R 2) (CH 2) p O (CH 2)
_r −, − CON (R ₂ ) (CH ₂ ) _p O (CH ₂ ) _r −, − SO ₂ N (R ₂ ) (CHR ₂ ) _p −,
_{- (CH 2) p (CHOH} ) s (CH 2) r - , and the like.

As an example of X ⁺ , -N ⁺ (R ₂ ) ₃ , -N ⁺ (CH ₂ CH
^{_{2 OCH 3) 3, -N +}} C 4 H 8 O (R 2). -N ⁺ (R ₂ ) (R ₂ ) (CH ₂ CH ₂ OCH ₃ ),
−N ⁺ C ₅ H ₅ , −N ⁺ (R ₂ ) (R ₃ ) (CH ₂ ) _p C ₆ H ₅ , −N ⁺ (R ₂ ) (R ₃ ) (R ₃ )
Etc. can be mentioned. Here, R ₂ and R ₃ each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (which may have a substituent), p, r and s each are 0 to 6 and q is 1 to
Twenty.

As an example of Y ⁻ , I ⁻ , Cl ⁻ , Br ⁻ , CH ₃ SO ₃ ⁻ , C
H ₃ -C ₆ H ₄ -SO _3- ^{and the} like can be mentioned.

Specific examples of the fluorine-based cationic activator preferably used in the present invention are given below, but the invention is not limited thereto.

[0048]

[Chemical 10]

[0049]

[Chemical 11]

[0050]

[Chemical 12]

In the present invention, it is particularly preferable to use a fluorine-based cationic activator containing at least one bond of —SO ₂ N (R ₂ ) — which is hardly soluble. Here, sparingly soluble means pure water at 23 ° C.
Add 2.0g of the activator to 100cc and stir for 1 hour at 23 ℃
Poorly soluble when it forms a precipitate after standing for 24 hours or when a floating substance is observed. For example, FK-1, FK-8, F
K-15, FK-16, etc. correspond, but are not limited to these and can be divided by the above test. Furthermore, the fluorine-containing surfactant represented by the following general formula (FK-S) is preferable.

[0052]

[Chemical 13]

In the formula, R ₄ is a hydrogen atom or a carbon atom of 1 to
5 represents an alkyl group. R ₅ , R ₆ and R ₇ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a hydroxyalkyl group. X ⁻ represents a counter ion of quaternary ammonium. n represents an integer of 1 to 10, m represents an integer of 1 to 6, l represents 0 or 1, and k represents an integer of 0 to 5. Examples of the alkyl group having 1 to 5 carbon atoms represented by R ₄ include a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group.

1 to ₅ carbon atoms represented by R ₅ , R ₆ and R ₇
Examples of the alkyl group of 5 include a methyl group, an ethyl group,
Examples thereof include a propyl group, a butyl group and a pentyl group.

Examples of the hydroxyalkyl group represented by R ₅ , R ₆ and R ₇ include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group and a hydroxybutyl group. Each of R ₅ , R ₆ and R ₇ is independent of each other and may be the same or different.

Examples of the counter ion of the quaternary ammonium represented by X ⁻ include Br ⁻ , Cl ⁻ , I ⁻ , CH ₃ SO ₃ ⁻ and 4-methyl.
Examples thereof include benzenesulfonate ion, CH ₃ COO ⁻ , NO ₃ ⁻ and benzenesulfonate ion.

Specifically, compounds other than those shown above are exemplified below.

[0058]

[Chemical 14]

[0059]

[Chemical 15]

[0060]

[Chemical 16]

[0061]

[Chemical 17]

In obtaining the fluorine residual ratio of the present invention, it is particularly advantageous to use a combination of those selected from these fluorine-containing anionic surfactants and those selected from fluorine-containing cationic surfactants.

The surfactants according to the present invention are, for example, US Pat. Nos. 2,559,751, 2,567,011 and 2,732,
398 publication, 2,764,602 publication, 2,806,866 publication,
2,809,998, 2,915,376, 2,918,501
Publications, 2,934,450 publications, 2,937,098 publications, 2,
957,031 publication, the same 3,472,894 publication, the same 3,555,089 publication, British patent 1,143,927 publication, the same 1,130,822 publication,
JP-B-45-37304, JP-A-47-9613, 49-13
4614 publication, 50-117705 publication, 50-117727 publication,
50-121243, 52-41182, 51-12392, British Chemical Journal (J. Chem. Soc.) 1950, page 2789, 195.
7 years, pages 2574 and 2640, American Chemical Journal (J. Amer. Chem. So
c.) 79, 2549, Oil Chemistry (J. Japan. Oil. Chemists Soc.) 12
Vol. 653, Journal of Organic Chemistry (J. Org. Chem.) Vol. 30, 3524 (1965
, Etc.) and the like.

Some of these fluorine-containing surfactants are available from Dainippon Ink and Chemicals, Inc.
egafac) F under the trade name Minnesota Mining and
Fluorad FC is a product name from Manufacturing Company, Monfor is a product name from Imperial Chemical Industry, and Zonyrus is a product name from Ei DuPont Nemeras & Company. Zonyls), and Licovet VP from Farbeberke Hoechst.
They are sold under the trade name E.

The total amount of the fluorine-containing cationic surfactant and the fluorine-containing anionic surfactant used in the present invention is 0.1 to 1000 mg per 1 m ² , and preferably 0.5 to 300 m.
g, more preferably 1.0 to 150 mg. Also, two or more of each may be used in combination.

In addition, a fluorine-based nonionic surfactant, a fluorine-based betaine surfactant, a hydrocarbon-based anionic surfactant, a cationic surfactant, a nonionic surfactant and a betaine surfactant are used in combination. You may.

The addition ratio of the fluorine-containing cationic surfactant and the fluorine-containing anionic surfactant according to the present invention is preferably 1:10 to 10: 1 in molar ratio, and further 3: 7 to 7 :.
3 is preferable.

In the present invention, the fluorine-containing cationic surfactant and the fluorine-containing anionic surfactant are not particularly limited to be added, but may be the surface protective layer on the image forming side of the light-sensitive material or the surface layer of the intermediate product. It is preferable. or,
It can also be used by overcoating on the surface layer.

These surfactants include alcohols such as methanol, ethanol, propanol and isopropanol, ketones such as acetone and methyl ethyl ketone, halogenated hydrocarbons such as methylene chloride and carbon tetrachloride, ethers such as diethyl ether and dioxane. It can be used by dissolving it in a solvent of aromatic hydrocarbons such as benzene, benzene and toluene.

Next, the development processing in the present invention means a color development processing step (35.0 ± 0.3 ° C., 45 seconds), a bleach-fixing processing step (35.0 ± 0.3 ° C., 45 seconds), a stabilization processing step or a water washing step. (30 to 34 ° C, 1 minute 30 seconds) and drying step (60 to 80 ° C,
A series of 60 seconds) is representative. As the processing liquid used in each step, those commercially available for processing color photographic light-sensitive materials can be used. Incidentally, even when the time required for each step is shortened or extended, it corresponds to the developing process here.

In the present invention, the coating amount of the binder is 1 m ²
A silver halide photographic light-sensitive material of 7.5 g or less is intended. If it exceeds this, it is not possible to form a thin film which is effective for rapid processing of silver halide photographic light-sensitive materials. In the present invention, the coating amount is
When the amount is 7.0 g / m ² or less, and further 6.0 g / m ² or less, the effect is greatly exhibited. However, in order to maintain the performance and physical properties required for silver halide photographic light-sensitive materials and finished photographs, the binder coating amount is 4.0 g / m ²
More preferably, it is more than 5.0 g / m ² .
In the present invention, it is preferable that at least one of the photographic constituent layers constituting the silver halide photographic light-sensitive material contains an organopolysiloxane.

The organopolysiloxane referred to here is formed of an organopolysiloxane skeleton and includes those having a structural unit represented by the following general formula (S1).

[0073]

[Chemical 18]

Here, R ₈ and R ₉ are hydrogen atoms, alkyl groups,
It represents an aryl group, and the alkyl group and the aryl group may be substituted with a substituent, and R ₈ and R ₉ may be the same or different. Examples of the alkyl group represented by R ₈ and R ₉ include a methyl group, an ethyl group and a propyl group, and examples of the aryl group include a phenyl group and the like. Preferred groups for R ₈ and R ₉ are methyl group and phenyl group, and particularly preferred group is methyl group.

Preferably, the following general formula (S2) is applied to both ends.
It has a terminal group represented by.

[0076]

[Chemical 19]

Here, R ₁₀ , R ₁₁ and R ₁₂ respectively represent a hydrogen atom, an alkyl group and an aryl group, the alkyl group and the aryl may be substituted with a substituent, and R ₁₀ , R ₁₁ and R ₁₂ are They may be the same or different. R
Examples of the alkyl group represented by ₁₀ , R ₁₁ and R ₁₂ include a methyl group and an ethyl group, and examples of the aryl group include a phenyl group. The alkyl group represented by R ₁₀ , R ₁₁ and R ₁₂ includes those substituted with a single or plural aryl groups (eg, phenyl group etc.), and also R ₁₀ , R ₁₁ and R ₁₂ The aryl group represented includes those substituted with a single or plural alkyl groups (eg, methyl group etc.) and the like. R ₁₀ , R ₁₁ and R
Preferred groups of ₁₂ are an alkyl group and an aryl group, and a methyl group is particularly preferred.

Among the organopolysiloxanes used in the present invention, the organic group bonded to the silicon atom forming the organopolysiloxane skeleton has an epoxy group, a fluorine-modified group, a vinyl group or a cyano group. Or a modified organopolysiloxane in which an epoxy group, a fluorine-modified group, a vinyl group or a cyano group is directly bonded to the above silicon atom and modified. Useful ones include those having a structural unit represented by the following general formula (I).

[0079]

[Chemical 20]

Here, R ₁₃ represents a hydrogen atom, an alkyl group, an aryl group, or — (R ₁₄ ) nA, R ₁₄ represents a divalent linking group, A represents an epoxy group, a fluorine-modified group, or vinyl. Represents a group and a cyano group. n represents 0 or 1.

Examples of the alkyl group represented by R ₁₃ include a methyl group and an ethyl group, and examples of the aryl group include a phenyl group. Preferred groups for R ₁₃ are a methyl group and a phenyl group, and a particularly preferred group is a methyl group.

The divalent linking group represented by R ₁₄ is preferably an alkylene group (eg, monomethylene group, dimethylene group, trimethylene group, etc.) or an arylene group (eg, phenylene group, etc.), 2 to 4 carbon atoms
Is preferable, and a dimethylene group and a trimethylene group are particularly preferable.

The epoxy group represented by A is, for example, ethylene oxide group (epoxyethyl group), trimethylene oxide group (1,3-epoxypropyl group), methylethylene oxide group (1,2-epoxypropyl group), etc. And a particularly preferred epoxy group is an ethylene oxide group (epoxyethyl group).

The fluorine-modified group represented by A includes a trifluoromethyl group, a difluoromethyl group, a monofluoromethyl group and the like, and a particularly preferable fluorine-modified group is a trifluoromethyl group.

N represents 0 or 1, and when A is an epoxy group, a fluorine-modified group or a cyano group, n is preferably 1. When A is a vinyl group, n is 0.
Is preferred.

The organopolysiloxane preferably used has an end group represented by the following general formula (II) at both ends.

[0087]

[Chemical 21]

Here, R ₁₅ , R ₁₆ and R ₁₇ are each a hydrogen atom, an alkyl group, an aryl group, or-(R ₁₄ ) n-.
A (R _14, A and n are respectively the same as R _14, A, and n in the general formula (I).) Represents, R _15, R
₁₆ and R ₁₇ may be the same or different. Examples of the alkyl group represented by R ₁₅ , R ₁₆ and R ₁₇ include a methyl group and an ethyl group, and examples of the aryl group include a phenyl group. R
_The alkyl groups represented by ₁₅ , R ₁₆ and R ₁₇ include those substituted with a single or plural aryl groups (eg phenyl group etc.) and the like, and are represented by R ₁₅ , R ₁₆ and R _17. The aryl group includes those substituted with a single or plural alkyl groups (eg, methyl group etc.).
Preferable groups of R ₁₅ , R ₁₆ and R ₁₇ are an alkyl group and an aryl group, and a methyl group is particularly preferable. The organopolysiloxane preferably used may have a structural unit represented by the following general formula (III).

[0089]

[Chemical formula 22]

Here, R ₁₈ and R ₁₉ each represent a hydrogen atom, an alkyl group or an aryl group, and R ₁₈ and R ₁₉ may be the same or different.

The alkyl group represented by R ₁₈ and R ₁₉ is preferably an alkyl group having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group.
Examples of the aryl group include a phenyl group and the like. The alkyl group represented by R ₁₈ and R ₁₉ includes those substituted with a single or plural aryl groups (eg, phenyl group etc.), and the aryl group represented by R ₁₈ and R ₁₉ is a single group. Alternatively, it also includes those substituted with a plurality of alkyl groups (eg, methyl group). R ₁₈ and R
Preferred groups for ₁₉ are methyl or phenyl groups.

The organopolysiloxane has a structural unit represented by the above general formula (I) and / or a structural unit represented by the general formula (III), and is further represented by the general formula (II). Those having an end group of
The terminal groups at both ends may be the same or different, but the same case is preferable. However, when the main chain is formed only from the structural unit represented by the general formula (III), at least one of R ₁₅ , R ₁₆ and R _{17 in} the terminal group represented by the general formula (II) is used. One is — (R ₁₄ ) nA.

Among the organopolysiloxanes represented by the general formula (I), the organopolysiloxane modified with an epoxy group is particularly preferably used.

Typical examples of the organopolysiloxane which can be used in the present invention are shown below. In addition, η is a viscosity measured using a rotational viscometer at 25 ° C., and the unit is centistokes (CS).

[0095]

[Chemical formula 23]

[0096]

[Chemical formula 24]

[0097]

[Chemical 25]

[0098]

[Chemical formula 26]

[0099]

[Chemical 27]

[0100]

[Chemical 28]

The method for producing these organopolysiloxanes is described, for example, in "Chemistry of the Silicone (Chapman and Hall 1951 Edition)" by EGRochou, pages 66-70, "Processing of Silicone Application ”(Kansai Plastic Technology Research Group 1954) 26
Pp. FG, A, Stone and VAG Graham, "Inorganic Polymers" (Academic Press 1962), pages 230-231, pages 288-295. , Japanese Patent Publication No. 35-10771, No. 43-28694, No. 45.
-14898, etc.
It can be synthesized by applying a method by addition reaction of olefins to siloxane containing H or a method by co-hydrolysis of each component organofluorosilane as shown in JP-B-36-22361. . Some of these organopolysiloxanes are available from Petrarch Systems, Inc. in the United States, Shin-Etsu Chemical Co., Ltd. in Japan, Toray Dow Corning Silicone Co., Ltd., and Toshiba Silicone It is also commercially available from K.K., and can be easily obtained.

The viscosity of the organopolysiloxane at 25 ° C. is about 10-100,000 as measured by a rotational viscometer.
It is preferred to indicate centistokes.

In order to incorporate the organopolysiloxane into the photographic constituent layer, there are a method of adding it to the coating solution in advance and a method of overcoating or permeating the organopolysiloxane, but the former is preferable in terms of production cost. As a method of adding to the coating liquid, a method of dispersing an organopolysiloxane in water or a hydrophilic colloid solution, for example, a gelatin solution in the presence of a dispersant, and further adding it to a desired photographic coating liquid. Alternatively, there is a method in which a gelatin solution for photography is dispersed in the presence of a dispersant and then coated as it is.

As the dispersant, a surfactant usually used for photography can be used and, for example, an anionic surfactant, a nonionic surfactant or a cationic surfactant is appropriately selected. Any thing can be used.

As a dispersing method, an ultrasonic homogenizer or a valve homogenizer can be used.

At the time of dispersion, a low boiling point solvent such as ethyl acetate, methanol or acetone, or tricresyl phosphate or the like is often used in order to facilitate the dispersion and control the dispersed particle size. A high boiling point solvent may be used.

The preferred particle size of the organopolysiloxane in the dispersed state is 0.1 to 10 μm.
If the particle size is too small, no effect on the slip property and scratch resistance can be seen, and if the particle size is too large, it devitrifies and is not preferable as a photographic material.

The refractive index of the organopolysiloxane used in the present invention is not particularly limited, but it is suitable that the measured value at 25 ° C. is usually about 1.320 or more and 1.685 or less, preferably 25 ° C. or more is 1.350 or more. Those within the range of 1.540 or less are effective. If the refractive index is smaller than 1.320 or larger than 1.685, it may affect the transparency of the applied photographic light-sensitive material, especially dried photographic light-sensitive material after photographic processing. is there.

In the present invention, the organopolysiloxane is preferably used in an amount of 0.001 g or more and 0.050 g or less, and 0.003 g or more and 0.020 g / m ^{2 of the} silver halide photographic light-sensitive material.
It is more preferably g or less.

Here, the photographic constituent layers constituting the silver halide photographic light-sensitive material include a silver halide emulsion layer and non-light-sensitive layers such as a protective layer, an intermediate layer, an antihalation layer and a back coat layer. . The organopolysiloxane may be used in any of the photographic constituent layers, but is particularly preferably used in the protective layer which is the outermost layer or the backcoat layer which is the outermost layer on the back surface side. In addition, when organopolysiloxane is used for the layer having a release surface of a release-type diffusion transfer type silver halide photosensitive material, excellent performance is obtained due to the fact that fluorine is unlikely to fall off when the organopolysiloxane is surrounded. Can be demonstrated.

The silver halide photographic light-sensitive material of the present invention comprises
At least one of the photographic constituent layers constituting the silver halide photographic light-sensitive material contains at least one hydrophobic compound having a solubility of 0.1 g or less in 100 g of pure water at 25 ° C. and having carbon as a main component. This is preferable because the residual fluorine rate is improved.

As used herein, "mainly composed of carbon"
This means that the main constituent of the compound is a carbon chain, and whether it is linear, branched, or cyclic,
It may be a complex thereof, and may be saturated or unsaturated. Further, at this time, a divalent linking group may be contained in this as long as the main component is a carbon chain, and in the case of a cyclic compound, it may be a heterocyclic compound. Further, the organic group may be substituted with a substituent.

The hydrophobic compound containing carbon as a main component which can be used in the present invention is a general compound used in a photographic light-sensitive material, for example, a coloring dye precursor (so-called coupler), a dye image stabilizer, an ultraviolet absorber, Not only a color mixing inhibitor, a high-boiling point solvent, a low-boiling point solvent, etc. are applied, but in addition, a hydrocarbon-based compound or a substitution product thereof can also be applied.

Preferred examples of the hydrocarbon-based hydrophobic compound that can be used in the present invention include compounds represented by the following general formula (P).

[0115]

[Chemical 29]

Preferred examples of the hydrophobic compound containing carbon as a main component which can be used in the present invention include compounds represented by the following general formulas (A) and (B).

[0117]

[Chemical 30]

In the formula, R ₂₀ and R ₂₁ each represent a secondary or tertiary alkyl group. However, the total number of carbon atoms of the alkyl groups represented by R ₂₀ and R ₂₁ is 20 or more. Examples of the secondary or tertiary alkyl group represented by R ₂₀ and R ₂₁ include sec-
A decyl group, a sec-dodecyl group, a t-dodecyl group and the like can be mentioned. The compound represented by the general formula (A) is a dialkylhydroquinone, and typical examples thereof are shown below, but not limited thereto.

The quinone form of the compound represented by formula (A) may be used in combination. The quinone compound may be added by spontaneously aerating the compound represented by the general formula (A) by air oxidation, or by adding a separately synthesized quinone compound.

[0120]

[Chemical 31]

The compound represented by the general formula (A) is usually
It is preferably contained in an amount of 01 to 0.05 g / m ² .

[0122]

[Chemical 32]

[In the formula, R ₂₂ and R ₂₃ represent an alkyl group having 8 to 24 carbon atoms. The alkyl group in the general formula may be linear or branched, and may have a substituent. Unsubstituted ones are preferred.

Next, typical examples of the compounds represented by the above general formula will be shown, but the compounds usable in the present invention are not limited by these.

[0125]

[Chemical 33]

These phthalic acid dialkyl esters are preferably used in an amount of 0.5% by weight or more and 10% by weight or less with respect to the hydrophilic colloid coated on the uppermost layer, and these phthalic acid dialkyl esters are used in silver halide photography. It is preferable to coat the photosensitive material within a range of from 4.5 mg to 90 mg per 1 m ² .

These can be synthesized by a general method. For example, phthalic acid or phthalic anhydride can be easily synthesized by a conventional esterification reaction, that is, by reacting with an aliphatic monohydric alcohol in the presence of a catalyst such as P-toluenesulfonic acid or sulfuric acid or a condensing agent.

In the present invention, it is preferable that the uppermost layer constituting the silver halide photographic light-sensitive material contains at least one compound represented by the following general formula [AS].

[0129]

[Chemical 34]

In the formula, R ₂₄ and R ₂₅ each represent an alkyl group having 1 to 5 carbon atoms, n represents an integer of 1 to 20, and k represents 1 or 2. A is-(C = O) -L-R ₂₆ (L is -O- or -N (R
₂₇₎ - represents, R ₂₆ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group, R ₂₇ represents a hydrogen atom, an alkyl group or an aryl group), - OV
(V is R ₂₆ or - (C = O) represents a -R _26, R ₂₆ is as defined _{above), - N (R 27)} (R 28) (R 27 is as defined above, R ₂₈ is a hydrogen atom, alkyl group, an aryl group, or - represents a _{(C = O) -R 26,} R 26 is as defined _{above), - P (oR 26)} (= O) (O) q-R 29
(Q represents 0 or 1, R ₂₆ has the same meaning as above, R ₂₉ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group) or a cyano group. B is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group,
Heterocycle or _{-C (R 24) (R 25} ) -Cn H 2 n + 1- k- (A) a group represented by _{k (R 24, R 25,} n, k and A are each as defined above ) Represents.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ₂₄ and R ₂₅ include methyl, ethyl, propyl, i-
Examples include propyl, butyl, s-butyl, pentyl, neopentyl and the like. n represents an integer of 1 to 20, preferably 2 to 15.

Of the groups constituting A, an alkyl group represented by R ₂₆ , an alkenyl group, a cycloalkyl group, an aryl group, an alkyl group represented by R ₂₇ , an aryl group, and an alkyl represented by R _28. Group, aryl group, alkyl group represented by R ₂₉ , cycloalkyl group, alkenyl group, aryl group,
Further, the alkyl group, alkenyl group, cycloalkyl group, aryl group and heterocyclic group represented by B include those having a substituent, respectively, and the substituent of the alkyl group is
Examples thereof include a halogen atom, a cycloalkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, a heterocyclic group, a cyano group, and the like. Among the above alkenyl groups, cycloalkyl groups, aryl groups, and heterocyclic groups, Examples of the substituent include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, a heterocyclic group, a cyano group and the like.

Examples of the alkyl group represented by R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ and B include methyl, ethyl, propyl, butyl, s-butyl, hexyl, 2-ethyl-hexyl, dodecyl, hexadecyl, Benzyl and the like,
Examples of the alkenyl group represented by R ₂₆ , R ₂₉ and B include allyl and the like, and examples of the cycloalkyl group represented by R ₂₆ , R ₂₉ and B include cyclohexyl and the like, R ₂₆ , Examples of the aryl group represented by R ₂₇ , R ₂₈ , R ₂₉ and B include phenyl and naphthyl.

The compound represented by the above general formula [AS] is
Further, a compound represented by the following general formula [AS-II] or a precursor thereof is preferable.

[0135]

[Chemical 35]

[0136] In the _{formula, R 24, R 25, R} 26, L and n have the same meanings as _{R 24, R 25, R 26} , L and n in the general formula [AS].

Typical examples of the compound represented by the general formula [AS] include H (1) to H (17) described in JP-A-62-172358, but the present invention is not limited to these. It is not limited to these.

The compound represented by the general formula [AS] basically includes the compounds described in JP-A-58-24141, and the synthesis method described in the same can be referred to.

The compound represented by the general formula [AS] is preferably contained in the uppermost layer constituting the light-sensitive material,
Usually, it is preferably contained in an amount of 0.01 to 0.05 g / m ² .

In the present invention, it is preferable that the uppermost layer of the silver halide photographic light-sensitive material contains at least one ultraviolet absorber. The ultraviolet absorber is well known in the art and any of them can be applied.

There are liquid ultraviolet absorbers and solid ultraviolet absorbers at room temperature, but the liquid ultraviolet absorbers may be used alone or in combination of two or more liquids.
Further, only the solid form may be used alone, or two or more solid form may be used in combination. Further, liquid and solid ones may be used alone, or two or more liquid and solid ones may be used in combination.

The UV absorber is preferably liquid at room temperature, particularly preferably the melting point of the UV absorber is 30 ° C. or lower, and even more preferably liquid at 15 ° C. The liquid ultraviolet absorber may be a single component or a mixture of several structural isomers.

The carbon-based hydrophobic compounds that can be used in the present invention can be dispersed singly or as a mixture of two or more kinds directly in water or a hydrophilic colloid solution, for example, a gelatin solution. Alternatively, it may be dissolved in a low boiling point solvent, a high boiling point solvent or a mixture of a low boiling point solvent and a high boiling point solvent, and then dispersed in water or the hydrophilic colloid solution in the presence of a dispersant.

As the dispersant, a surfactant usually used for photography can be used. For example, from an anionic surfactant, a nonionic surfactant, an amphoteric surfactant or a cationic surfactant. A 0 / W type emulsion is preferably prepared using an ultrasonic homogenizer that is appropriately selected.

Then, this dispersion is added to a gelatin solution so as to be contained in at least one layer of the silver halide photographic light-sensitive material, preferably the protective layer which is the uppermost layer. It is possible to obtain a silver halide photographic light-sensitive material that easily slips and is not easily scratched by the contact of

As the high boiling point solvent, for example, US Pat.
No. 322,027. Further, as the low boiling point solvent, for example, methanol, ethanol, acetone,
Examples thereof include ethyl acetate and ethyl cellosolve. Even if these compounds used in the present invention are used alone or in combination with a high boiling point solvent and a low boiling point, the effect is hardly changed.

When these compounds are used in a weight ratio of 1 to 10% with respect to a water-soluble binder such as gelatin constituting the layer, the surface characteristics of the silver halide photographic light-sensitive material become particularly preferable characteristics. .

When the silver halide photographic light-sensitive material of the present invention is used in a color photographic light-sensitive material, an aromatic primary amine developer (for example, p-phenylenediamine derivative or aminophenol derivative) is used in color development processing. Such)
A dye-forming coupler is used which forms a dye by a coupling reaction with the oxidant. The dye-forming couplers are usually selected for each emulsion layer so that a dye that absorbs the light in the light-sensitive spectrum of the emulsion layer is formed, and in the blue-sensitive emulsion layer, the yellow dye-forming coupler is green. A magenta dye-forming coupler is used in the sensitive emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, the silver halide photographic light-sensitive material may be produced by a method different from the above combination depending on the purpose.

It is desirable that these dye-forming couplers have a group having a carbon number of 8 or more, which is called a ballast group, in the molecule, which makes the coupler a specific diffusion. Also, these dye-forming couplers, even though they are 4-equivalent, need to reduce 4 molecules of silver ion to form 1 molecule of dye,
It may be either dimeric, which only needs to reduce two molecules of silver ions.

As the yellow dye-forming coupler, various acylacetanilide type couplers can be preferably used. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous.

As the magenta dye forming coupler, 5-pyrazolone type couplers, pyrazolobenzimidazole type couplers, pyrazoloazole type couplers and open chain acylacetonitrile type couplers can be preferably used.

As the cyan dye forming coupler, a naphthol type coupler and a phenol type coupler can be preferably used.

The compound such as the dye-forming coupler of the light-sensitive material of the present invention is usually used in combination with a high-boiling point organic solvent having a boiling point of about 150 ° C. or higher and a water-insoluble polymer in combination with a low-boiling point and / or water-soluble organic solvent, if necessary. It is then dissolved and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant, and then added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be added at the same time as the dispersion or dispersion.

The high-boiling organic solvent is preferably a compound having a dielectric constant (at 30 ° C.) of 6.5 or less. For example, esters such as phthalic acid ester and phosphoric acid ester having a dielectric constant of 6.5 or less,
Organic acid amides, ketones, hydrocarbon compounds and the like.
More preferably, a high boiling point organic solvent having a dielectric constant of 6.5 or less and 1.9 or more and a vapor pressure at 100 ° C. of 0.5 mmHg or less, among these, more preferably phthalic acid esters or phosphoric acid esters, and most preferably It is a dialkyl phthalate having an alkyl group having 9 or more carbon atoms. Further, the high boiling point organic solvent may be a mixture of two or more kinds. These high-boiling organic solvents are generally used in an amount of 0 to the coupler.
Used in a proportion of 400% by weight. It is preferably 10 to 100% by weight based on the coupler.

The present invention effectively exhibits its effect when it is used for a color photographic paper directly provided for viewing, and it may be a monochromatic one or a multicolored one.

As the silver halide used in the light-sensitive material of the present invention, any silver halide such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide and silver chloride which is usually used in silver halide emulsions can be used. However, it is preferable that the silver chloride content is 99.0 mol% or more, the silver bromide content is 1 mol% or less, and the silver iodide content is 0.1 mol% or less. . Furthermore, the silver bromide content is preferably 0.01 to 0.05.
It is mol% of silver chlorobromide.

The silver halide grains may be used alone or in combination with other silver halide grains having different compositions. Further, it may be used as a mixture with silver halide grains having a silver chloride content of 99.0 mol% or less.

Further, in a silver halide emulsion layer containing silver halide grains having a silver chloride content of 99.0 mol% or more, the silver chloride content in all silver halide grains contained in the emulsion layer is The proportion of silver halide grains of 99.0 mol% or more is 60% by weight or more, preferably 80% by weight or more.

The silver halide emulsion used in the present invention is
It is chemically sensitized by a sulfur sensitizing method, a selenium sensitizing method, a reduction sensitizing method, a noble metal sensitizing method, or the like. Further, a dye known as a sensitizing dye in the photographic industry can be used to optically sensitize a desired wavelength range.

The binder used in the light-sensitive material of the present invention is preferably gelatin, and may be lime-processed gelatin or acid-processed gelatin.
Further, beef bones, beef hide, gelatin produced from any one of pig skins may be used, but beef bones, lime-processed gelatin produced from pig hides, and more preferably in the uppermost layer, It is a lime-processed gelatin produced from pig skin.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material are hardened by using a hardener which crosslinks the binder (or protective colloid) molecule and enhances the film strength, alone or in combination. The hardener is preferably added in such an amount that the photosensitive material can be hardened to the extent that it is not necessary to add the hardener to the processing liquid, but it is also possible to add the hardener to the processing liquid.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and / or an irradiation prevention layer. In these layers and / or in the emulsion layer, a dye which flows out from the color light-sensitive material or is bleached during the development process may be contained.

A matting agent can be added to the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material for the purpose of reducing the gloss of the light-sensitive material, enhancing the writing property, and preventing sticking between the light-sensitive materials. . Also, a slip agent can be added to reduce sliding friction.

An antistatic agent may be added to the light-sensitive material for the purpose of antistatic. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be used to protect the emulsion layer and / or the emulsion layer on the side of the support other than the emulsion layer. It may be used for the colloid layer.

The photographic emulsion layer and other layers of the silver halide photographic light-sensitive material of the present invention are baryta paper or paper laminated with α-olefin polymer or the like, and a paper support from which the α-olefin layer can be easily peeled off from the paper support. , Plastic support such as synthetic paper, film made of semi-synthetic or synthetic polymer such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide and white pigment coated reflective support It can be applied to the body, rigid body such as glass, metal, pottery, etc. Also, a thin reflective support having a thickness of 120 to 160 μm can be used.

The support used in the present invention may be either a reflective support or a transparent support, may contain a white pigment in the support for imparting reflectivity, or may contain a white pigment on the support. A hydrophilic colloid layer may be provided by coating.

As the white pigment, inorganic and / or organic white pigments can be used, preferably inorganic white pigments. Examples of such white pigments include alkaline earth metal sulfates such as barium sulfate. Examples thereof include alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, synthetic silicate silicas, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc and clay. Barium sulfate and titanium oxide are preferably used as the white pigment.

In the silver halide photographic light-sensitive material of the present invention, the support surface is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, and then directly or undercoat layer (adhesiveness of the support surface, charging It may also be applied via one or more subbing layers) for improving anti-preventive properties, dimensional stability, abrasion resistance, hardness, antihalation properties, friction properties and / or other properties.

At the time of coating the silver halide photographic light-sensitive material of the present invention, a thickener may be used to improve coatability. As a coating method, extrusion coating and curtain coating which can simultaneously coat two or more layers are particularly useful.

The color developing agent used in the color developing solution in the present invention includes known ones widely used in various color photographic processes.

In the present invention, the color developing process may be immediately followed by a processing solution having a bleaching ability, but the processing solution having a bleaching ability may be a processing solution having a fixing ability (so-called bleach-fixing solution). . A metal complex salt of an organic acid is used as the bleaching agent used in the bleaching step.

[0172]

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

Example 1 A paper support was prepared by laminating high density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side where the emulsion layer was coated, a molten polyethylene containing a surface-treated anatase type titanium oxide dispersed in a content of 15% by weight was laminated to prepare a reflective support.

Each layer having the following constitution was coated on this reflective support to prepare a multilayer silver halide photographic light-sensitive material, Sample 101. The coating liquid was prepared as follows.

Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (ST-2) 6.67 g, additive (HQ-1) 0.67 g and high 60 ml of ethyl acetate was added to 6.67 g of boiling point organic solvent (DNP) to dissolve, and this solution was dissolved in 15% of surfactant (SU-1) 9.5 m.
A yellow coupler dispersion was prepared by emulsifying and dispersing in 220 ml of 10% gelatin aqueous solution containing l using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions to prepare a coating solution for the first layer. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. In addition, (H-1) was added to the second and fourth layers and (H-2) was added to the seventh layer as a hardening agent. As the coating aid, surfactants (SU-2), (S
U-3) was added to adjust the surface tension.

The layer structure is as shown in the table below.

[0177]

[Table 2]

[0178]

[Table 3]

[0179]

[Chemical 36]

[0180]

[Chemical 37]

[0181]

[Chemical 38]

[0182]

[Chemical Formula 39]

[0183]

[Chemical 40]

(Preparation of blue-sensitive silver halide emulsion) In 1000 ml of 2% gelatin aqueous solution kept at 40 ° C., the following (A solution) and (B solution) were added over 30 minutes while controlling pAg = 6.5 and pH = 3.0. At the same time, and then add the following (C solution) and (D solution) to pA
Simultaneous addition was carried out over 180 minutes while controlling g = 7.3 and pH = 5.5. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.07 g Water added 200 ml (Solution B) Silver nitrate 10 g Water added 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 2.10 g Water added 600 ml (Solution D) After adding 300 g of silver nitrate and adding 600 ml of water, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with a gelatin aqueous solution to obtain an average particle size. A monodisperse cubic emulsion EMP-1 having a diameter of 0.85 μm, a coefficient of variation (S / R) = 0.07 and a silver chloride content of 99.0 mol% was obtained.

The above emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B1).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitization Dye BS-2 1 × 10 ⁻⁴ mol / mol AgX (preparation method of green-sensitive silver halide emulsion) (solution A) and (B
(Liquid) and the addition time of (C liquid) and (D liquid) are changed in the same manner as EMP-1, except that the average particle size is 0.43 μm.
m, coefficient of variation (S / R) = 0.07, silver chloride content 99.0 mol%
A monodisperse cubic emulsion EMP-2 of was obtained.

For EMP-2, the following compounds were used.
Chemical ripening was carried out at 120 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G1).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (red Method for preparing sensitive silver halide emulsion) (solution A) and (B)
The average particle size is 0.50 μm in the same manner as EMP-1 except that the addition time of (solution) and the addition time of (solution C) and (solution D) are changed.
m, coefficient of variation (S / R) = 0.08, silver chloride content 99.0 mol%
To obtain a monodisperse cubic emulsion EMP-3.

For EMP-3, the following compounds were used.
Chemical ripening at 90 ° C for 90 minutes to give a red-sensitive silver halide emulsion (E
m-R1) was obtained.

Sodium thiosulfate 1.8 mg / mol AgX Chloroauric acid 2.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX

[0192]

[Chemical 41]

[0193]

[Chemical 42]

The color light-sensitive material sample thus obtained was sample No. It was 101.

Next, the seventh layer (protective layer) used in Sample 101
Samples except that the constituent compounds of are changed as shown in Table 4 below.
Samples are prepared in the same manner as in 101, and samples 102 to 12
It was set to 5.

Table 4 also shows the residual fluorine percentage after the development treatment of the sample, which was measured as described above.

[0197]

[Table 4]

[0198] If the compound of the seventh layer (protective layer) needs to be emulsified and dispersed, it was emulsified and dispersed by the following method.

(Emulsification Method of Organopolysiloxane) The organopolysiloxane used in the seventh layer (protective layer) of Sample 116 was emulsified and dispersed as follows to prepare the specified coating amount, and then the 7th layer was formed. It was mixed with the layer coating solution.

(Solution A) Organopolysiloxane S-19 28.8 g Ethyl acetate 55.8 cc (Solution B) Gelatin 14.2 g Emulsification stabilizer SU-2 (20% solution) 5.0 cc Water 171 cc (Solution A) and (Solution B) After being dissolved under heat retention of 40 ° C., each was mixed and stirred, and then emulsified and dispersed by an ultrasonic homogenizer to adjust the particle size of dispersed particles to 0.3 μm. The method for measuring the dispersed particles here can be easily measured by a method well known in the art. After completion of the emulsification dispersion, water was added to the emulsification dispersion to make 280 cc. At this time, it does not matter whether or not a means for completely evaporating ethyl acetate in the emulsified dispersion liquid is added before finishing by adding water, or separately.

For Samples 117 and thereafter, emulsion dispersion was carried out by the same method as above except that the compound used in the seventh layer (protective layer) was simply changed. However, the amount of ethyl acetate may be appropriately adjusted in order to adjust the particle size of the dispersed particles.

The compounds of the seventh layer (protective layer) used here are as follows.

[0203]

[Chemical 43]

(Various Performance Tests) Two samples each were prepared and subjected to optical wedge exposure with an exposure time of 0.5 seconds by an ordinary method, and then development processing was carried out in the following development processing step B.

(Processing Step B) Processing Step Processing Temperature Time Color Development B 35.0 ± 0.3 ° C. 45 seconds 162 ml / m ² Bleach-fixing B 35.0 ± 0.5 ° C. 45 seconds 216 ml / m ² Washing B 30-34 ° C. 90 seconds 248 ml / m ² Drying 60-80 ° C 60 seconds The composition of the developing solution is shown below.

Color developer B tank liquid Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediamine Tetraacetic acid 1.0 g Catechol-3,5-diphosphonate disodium 1.0 g N-Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 4.5 g Optical brightener (4,4 ′ -Diaminostilbene sulfonic acid derivative) 1.0 g Potassium carbonate 27 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 10.60.

Color developer B replenisher Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium sulfite 0.4 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediaminetetraacetic acid 1.0 g Catechol-3, 5-Diphosphonate disodium 1.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 8.0 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.3 g Potassium carbonate 30 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 10.60.

Bleach-fixing solution B Tank solution and replenishing solution Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Adjust to 1 liter and adjust to pH = 5.7 with potassium carbonate or glacial acetic acid.

Washing solution B Tank solution and replenishing solution 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0g Fluorescent brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.5g Add water to make the total volume 1 liter and adjust pH to 7.0 with sulfuric acid or potassium hydroxide. .

The following performance evaluation test was conducted on the treated sample obtained by the above treatment.

(Sample Surface Adhesion Test) Samples are bundled by superimposing the emulsion surfaces on each other or the emulsion surface and the back surface, respectively. After fixing it, 40 ℃ 80%
It was left for 15 hours under the condition of RH. After that, the sample in which the sample surfaces were stuck to each other was peeled off, and the following five-grade evaluation from 1 to 5 was performed by feeling the resistance at that time. The closer to 1, the better, and the closer to 5, the worse.

1 ... Sample surface is not stuck 2 ... Intermediate between 1 and 3 3 ... Resistive enough to make a noise when peeling 4 ... Intermediate between 3 and 5 5: The sample surfaces are stuck together and cannot be peeled off.

(Slidability test) A sample was set in a "pull universal tester" manufactured by Tester Sangyo Co., Ltd. by a prescribed method, and 50
The weight of g was added, and the coefficient of dynamic friction when the sample surface and the plate of Bakelite resin were slid together was measured by a conventional method. The slip property was evaluated by this dynamic friction coefficient. It indicates that the smaller the dynamic friction coefficient, the better the slipperiness.

(Conveying Practical Test in Automatic Developing Machine) Separately from the above sample, a silver halide photographic light-sensitive material (roll color paper) before development processing is specified by Konica Nice Print System, paper processor "NPS-602QA". Print processing was performed according to the method. The occurrence frequency of transport stop failure due to transport failure during continuous processing was classified as follows, and the transportability was subjectively evaluated.

1 ... No failure occurrence per 5000 prints 2 ... 〃 1-2 times 3 ・ ・ ・ 〃 3-4 times 4 ・ ・ ・ 〃 5-4 times is a problem in practical use.

Using the print samples obtained when continuous processing was carried out in the conveyance practical test in the above-mentioned automatic developing machine, the stickiness test and the slip property test of the sample surface were evaluated by the same method as above. .

Based on the evaluation results before the continuous treatment, the surface property evaluation after these continuous treatments was relatively evaluated by ◯, Δ, and ×. A circle is equivalent to the standard, a triangle is slightly inferior to the standard, and a cross is inferior to the standard.

The results are shown in Table 5.

[0219]

[Table 5]

As is clear from Table 5, the comparative samples cannot be denied deficiency in surface properties such as scratch resistance, sticking property, and slip property and deterioration of surface properties during continuous treatment.

However, it is understood that all of these performances are improved in the sample of the present invention. This effect cannot be achieved by each individual technology, and is of course not a total sum of the effects of each technology, but an improvement effect that cannot be conceived from the conventional technology.

Regarding the samples of the present invention, no abnormalities in basic photographic performance (sensitivity, tone, fog, etc.) were observed.

Example 2 A sample was prepared in the same manner as in Example 1 except that the following three types of support were used.

[0224]

[Table 6]

The SRa value represents the smoothness of the surface of the support, as described in JP-A 1-173030, and the smaller the value, the higher the smoothness. This measuring method is described in the same publication.

When the obtained sample was evaluated in the same manner as in Example 1, the effect of the present invention was obtained.

Example 3 A support for photographic printing paper was prepared by the following method.

The bleached sulfite pulp is beaten to about 40 ° SR and to this is added pulp to 2% petroleum resin size, and pulp to 1% starch size. Then, a resin mixture containing 1 part of vinylcyclohexene diepoxide and 7 parts of styrene-maleic anhydride copolymer was added to a solid content of 1% of pulp.
It was added, paper was made to a weight of 150 g / m ² , and 0.5 gm ^{2 of} gelatin was further attached in a tab size.

[0229] To this, a solution prepared by mixing glossy variator, mat variator, gelatin, citric acid, chrome alum and the like was applied so that the dry weight was 15 gm ² . The support thus produced is generally called a baryta base paper.

Samples were prepared in the same manner as in Example 1 except that the baryta base paper prepared in this manner was used.

When the obtained sample was evaluated in the same manner as in Example 1, the effect of the present invention was obtained.

Example 4 The following test was conducted using the sample prepared in Example 1.

[0233] Two samples each were prepared, and the exposure time was determined by a conventional method.
After light wedge exposure for 0.5 seconds, development processing was performed in the following development processing step A.

(Treatment Step A) Treatment Step Treatment Temperature Time Replenishment Amount Color Development A 38.0 ± 0.3 ° C. 20 seconds 80 ml / m ² Bleach-fix A 35.0 ± 0.5 ° C. 20 seconds 120 ml / m ² Water A 30-34 ° C. 60 seconds 150 ml / m ² Dry 60-80 ℃ 30 seconds Color developer A tank liquid Pure water 800 ml Tritylenediamine 2 g Diethylene glycol 10 g Potassium bromide 0.01 g Potassium chloride 3.5 g Potassium sulfite 0.25 g N-ethyl-N- (β-methanesulfonamidoethyl) ) -3-Methyl-4-aminoaniline sulfate 6.0g N, N-diethylhydroxylamine 6.8g Triethanolamine 10.0g Diethylenetriaminepentaacetic acid sodium salt 2.0g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative ) 2.0 g Potassium carbonate 30 g Add water to bring the total volume to 1 liter, and adjust to pH = 10.10.

Color developer A replenisher Pure water 800 ml Triethylenediamine 3 g Diethylene glycol 10 g Potassium sulfite 0.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 10.0 g N, N -Diethylhydroxylamine 6.0 g Triethanolamine 10.0 g Diethylenetriamine pentaacetic acid sodium salt 2.0 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 2.5 g Potassium carbonate 30 g Add water to bring the total volume to 1 liter. Adjust to 10.60.

Bleach-fixing solution A Tank solution and replenishing solution Diethylenetriamine pentaacetate ammonium ferric dihydrate 65 g Diethylenetriamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 5-Amino-1,3,4-thiadiazole-2-thiol 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Water is added to bring the total volume to 1 liter, and the pH is adjusted to 6.5 with potassium carbonate or glacial acetic acid.

Washing solution A Tank solution and replenishing solution Orthophenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-Methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Fluorescence Brightener (Tinopearl SFP) 2.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8 g BiCl3 (45% aqueous solution) 0.65 g MgSO4 / 7H2O 0.2 g PVP (polyvinylpyrrolidone) 1.0 g Ammonia water (25% ammonium hydroxide) Aqueous solution) 2.5 g Nitriloacetic acid trisodium salt 1.5 g Add water to make the total volume 1 liter, and adjust the pH to 7.5 with sulfuric acid or aqueous ammonia.

A performance evaluation test similar to that of Example 1 was conducted on the treated sample obtained by the above treatment.

As a result, the effect of the present invention was confirmed.

(Example 5) The center surface average roughness of the paper support used in Example 1 was 0.13 µm.

The method of measuring the average roughness of the center plane here is well known, but it is described in detail in JP-A No. 1-173030.

A sample was prepared in the same manner as in Example 1 except that the following support was used.

As the support, high-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g / m ² to prepare a polyethylene resin-coated paper. However, on the side on which the emulsion layer was coated, melted polyethylene containing 15% by weight of surface-treated anatase type titanium oxide dispersed therein was laminated, and a reflection support was prepared. At this time, high density polyethylene was laminated such that the center line average roughness was 0.11 μm.

The center line average roughness is as described above, but it represents the smoothness of the support surface, and the smaller the value, the higher the smoothness.

When the obtained sample was evaluated in the same manner as in Example 1, the effect of the present invention was obtained. Also,
When the organopolysiloxane of the present invention used for the seventh layer (protective layer) was reduced by 40% with respect to the amount used in Example 1, the same evaluation as in Example 1 was carried out. The effect of the invention was seen.

[0246]

EFFECTS OF THE INVENTION According to the present invention, even in the case of a printed photograph using a silver halide photographic light-sensitive material in which the coating amount of a binder is reduced, the surface slipperiness, stickiness and stickiness are improved, and glossiness and the like are improved. It is possible to obtain an excellent printed photograph in which surface characteristics and image quality are not deteriorated and surface characteristics are not deteriorated even in continuous processing.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshihiro Mochizuki 1st Sakura-cho, Hino City, Tokyo Konica Stock Company In-house

Claims (4)

[Claims] 1. A fluorine-containing surfactant is contained, the total amount of binder is 7.5 g / m ² or less, and 50% or more of the fluorine atoms present on the extreme surface on the image forming side before development are developed. A silver halide photographic light-sensitive material characterized by remaining on the surface after processing. 2. A fluorine-containing surfactant represented by the following general formula (FA) and a fluorine-containing surfactant represented by the following general formula (FK) are contained. The silver halide photographic light-sensitive material according to claim 1. In formula (FA) (Cf)-(Y) _n , Cf represents an n-valent group containing at least 3 fluorine atoms and at least 2 carbon atoms, and Y represents -COOM,-.
SO ₃ M, represents an -OSO ₃ M or -P (= O) (OM) 2. M represents a hydrogen atom or a cation such as an alkali metal or a quaternary ammonium salt, and n is 1 or 2. General formula (FK) Rf'-LX ⁺ Z ^-In formula, Rf 'represents a C1-C20 hydrocarbon group and at least one hydrogen atom is substituted by the fluorine atom.
L represents a chemical bond or a divalent group. X ⁺ is a cation,
Z ⁻ represents a counter anion. 3. The silver halide photographic light-sensitive material according to claim 1, wherein at least one of the photographic constituent layers constituting the silver halide photographic light-sensitive material contains an organopolysiloxane. 4. The outermost surface layer of the photographic constituent layers constituting the silver halide photographic light-sensitive material is at least one kind at 25 ° C.
4. The silver halide photographic light-sensitive material according to claim 1, which has a solubility of 0.1 g or less in 100 g of pure water and contains a hydrophobic compound mainly containing carbon.