JPH02191940A - Direct positive photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the high max. image density and the low min. image density by incorporating at least one kind of the sensitizing dyestuff expressed by the specific formula into at least one layer of emulsion layers. CONSTITUTION:At least one kind of the sensitizing dyes expressed by the formula I is incorporated into at least one layer of the emulsion layers contg. internal latent image type silver halide particles. In the formula, Y denotes a sulfur atom or selenium atom. W<1>, W<2>, W<3>, W<4> respectively denote a hydrogen atom, halogen atom, heterocyclic group such as substd. or unsubstd. alkyl group or alkoxy group. W<1> and W<2>, W<2> and W<3>, W<3> and W<4> may respectively form a benzene ring. R<1> and R<2> respectively denote a substd. or unsubstd. alkyl group, where at least one thereof denotes a hydroxylalkyl group, carboxyalkyl group or sulfoalkyl group. R<2> denotes a hydrogen atom or substd. or unsubstd. alkyl group or aryl group. X is a group for obtaining charge balance. The compd. of the specific formula forms an intramolecular salt when there is no X.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a direct positive photographic light-sensitive material, and more particularly to a direct positive photographic light-sensitive material that has excellent image discrimination.

[Conventional technology]

Photographic methods that provide direct positive images without the need for reversal processing steps or negative film are well known.

Methods used to create positive images using conventionally known direct positive silver halide photographic materials can be mainly divided into two types in consideration of their practical usefulness.

The first type uses a silver halide emulsion that has been fogged in advance and creates a positive image directly after development by destroying the fog nuclei (m-image) in the exposed area using solarization or the Burschel effect. It's something you get.

The second type uses an internal latent image type silver halide emulsion that has not been fogged in advance and directly obtains a positive image by performing surface development after or while performing fogging treatment after image exposure. .

The above-mentioned internal latent image type silver halide photographic emulsion is a type of silver halide photographic emulsion that has photosensitive nuclei mainly inside the silver halide grains and a latent image is mainly formed inside the grains upon exposure. means.

As mentioned above, as a means to directly generate Capri bales, there is a method of applying a second exposure to the entire surface of the nine layers, which is generally called the F-fogging method (for example, the British patents /, /yo/, 3
1/3) and a nucleating agent (n
A method for using a nucleating agent is known. For this method, see the example ``Search Disclosure'' (I also search disclosure).
sclosure )ig 1st! /Makifu/3162(/
76-7? Truly described.

The second type of method is generally more sensitive than the first type of method and is suitable for applications requiring high sensitivity, and the present invention relates to this latter type. .

Many techniques are already known in this technical field. For example, US Patent No. 92°230
No., IWJ No. λ, 4L46. ri No. 57, same No. ko.

11Y7.176 issue, same acx, try, yrJ issue,
Same No. 3.377.322, Same No. J, 7A/, -6
No. 6, No. 3, 76/, 276, No. 3", 7ri,
g, No. 177 and British License No. 1. /! /, 363
No., same @/, /jO,! ! No. 3 (1.0//, 01s
λ) The main ones are those described in each specification, etc.

Are these known methods? When used, it is possible to create a relatively high-sensitivity photographic material for a direct positive type.

For details on the direct positive image formation mechanism, see
T, )i, James II [The Theory of the Photographic Process J('I"he'l'he
ory of the Photographic P
roces 8) 1st edition, Chapter 7/pages 1-/23, and U.S. Pat. No. 3,71,/276.

In other words, due to the narrow-plane desensitization effect caused by the so-called internal m-image generated inside the silver halide by the initial imagewise exposure, capri nuclei are selectively generated only in the precious silver halide grains in the non-m element. Then, the usual so-called surface development treatment'? It is believed that by applying this, a photographic image (IK contact positive) is formed on the original part.

[Problem that the invention attempts to solve]

Direct positive Ll using such optical fogging method or chemical fogging method! In 1ltaiI molding, the development speed is slower and the processing time is longer than in the case of normal negative molding, so conventional methods have been to shorten the processing time by lowering the pH and/or temperature of the developer. It was getting worse. but,
Generally, when the pH or liquid temperature is high, the minimum S density of a direct positive image obtained increases. Under the fcIQip)i conditions, the main developing system is likely to deteriorate due to air oxidation, and as a result, the developing activity significantly decreases over time.

Other methods for avoiding the maximum concentration while keeping the minimum degree of the direct positive IfiI image small include those using hydroquinone derivatives (US Pat. Although compounds using Kuramono (time opening N60-/7θg≠3) are known, the effects of using these compounds are small. However, no technique has been found that can effectively increase the maximum density of a positive image without directly increasing its minimum IIk degree.

However, there are techniques that can provide a sufficient maximum image density even when processing with the current liquid.

Next, with this original fogging method, there is a problem in that the gradation is soft when forming a 1f''fiJrtt image using a chemical fogging method. This is noticeable in the highlight areas, and the next image formed using this method has the disadvantage that splint reproduction tends to be insufficient.

In order to solve this problem, methods for obtaining a hard Ill contact photosensitive material include a method of monodispersing silver halide grains, and a method of adding polyvalent metal ions to silver halide grains. Doping 10,000 @<VS3.3/s7,771
．． J, Ko♂7. /JA), and methods of adjusting the sensitization method of the core in so-called core/shell emulsions (US≠03!/1j) are known, but the effects of these methods are still not sufficient. do not have.

Therefore, the first object of the present invention is to produce an Il close-up image* that has a low minimum image density while maintaining a high maximum image density.
1- To provide a direct positive photographic light-sensitive material.

A second object of the present invention is to provide a direct positive photographic photographic material that provides a hard direct positive photograph.

[Defined means to solve Section M]

The above-mentioned object of the present invention is to provide a photographic light-sensitive material having at least one emulsion layer containing internal latent image type silver halide grains which have not been fogged in advance, at least one layer of the emulsion I- having the following general formula (I). This was achieved by a direct positive photographic light-sensitive material characterized by having at least /al'kt of a sensitizing dye represented by:

General formula (I) Y represents a sulfur atom or a selenium atom.

Wl, Wl, Vl'', W' 4*+substituted hydrogen atom, halogen atom, substituted or device 1 negative alkyl group, substituted or unsubstituted W1 alkoxy group, substituted or unsubstituted aryl group, If substituted or Unsubstituted or unsubstituted loxy group, hydroxy group, carboxy group, substituted or unsubstituted W1.
ta represents an alkoxycarbonyl group, acyloxy group, acylamino group, acyl group, ra, substituted or unsubstituted carbamoyl group, hetero y1 group; may be formed.

R1 and R represent each a negative or unsubstituted alkyl group, provided that at least one of them represents a hydroxyalkyl group, a carboxyalkyl group, or a sulfoalkyl group.

R1 represents a hydrogen atom, a substituted or unstirred alkyl group, W, or a stirred or unstirred aryl group.

X is a group for charge balance.

In the absence of X, the compounds of general formula (I) form internal salts.

First, the internal latent image type silver halide grains which are not fogged in advance and are used in the present invention will be explained.

The particles preferably have a so-called core/shell structure.

The core particles may be formed by a conversion type, or one or more types of chemical sensitization such as ordinary gold sensitization, sulfur sensitization, reduction sensitization, etc. may be used, or no chemical sensitization may be used. , or may be doped with metals such as iridium, palladium, and rhodium.

Although the shell does not need to be chemically sensitized, it is preferable to chemically sensitize it as described above.

The unfogged internal latent image type silver halide emulsion used in the present invention is an emulsion containing silver halide in which the surfaces of silver halide grains are not fogged in advance and latent images are mainly formed inside the grains. However, more specifically, 0.5 to 3 g of silver halide emulsion is deposited on a transparent support.
1rd2 cloth and 0. Exposure was performed for a fixed time of 10 to 10 seconds, and development was performed at 71°C for 5 minutes in the following developer mA (internal type developer), and the maximum density measured by the usual photographic density measurement method was the same as above. Apply the amount lW
The silver halide emulsion was exposed in the following developer solution B (
The maximum # degree obtained when developing for 4 minutes at 0°C in a surface type developer), at least! Preferably, those with a degree a are twice as large, and more preferably, those with a concentration that is at least 70 times greater.

Narrow surface developer B Metol -0jp2-Ascorbine #j! 10f NaB(J2 ・!) 12(J j
! j'KBr
/p Add water /It internal developer A Metol λ Risa sulfate soda (anhydrous) Tapop hydroquinone
tp Soda carbonate (-water salt)
! Ko, zpKk3r
111KI
O,! P Add water and l
For example, British Patent No.
, oli, otco, U.S. Patent No. 2. ! 92°λ5o4
j, direction 2. μ56. Conversion type silver halide emulsions and core/shell type silver halide emulsions which are described in specifications such as Tada No. 3 can be mentioned.As the core/shell type silver halide emulsions, Kaisho≠7-32♂13
No., Dokei 7-3ariμ No., Dokei J″--/31I7.2
/ issue, same! No. 3-40222, No. j-3-6421I, No. 1ffl j J-44727, No. 3-40222, No. 3-6421I, No. 3-40222, No. 3-6421I, No. 1ffl j J-44727, No. 7-/J6
1. ≠ / issue, same j! -7021/No. J9-201r
j4AO issue, same! Tar J/G/JA No. 6O-107
AIAI No. 7.2j No. 7, No. 6/--7
≠! No., same t/-J/37, 5th T-IR 3rd issue,! -1-1≠/No.2, same ♂-7≠7! No., direction
-t23j, I? l] Jzaichi 1orzλ1 No. 1, patent application Shoti-36 Ko2 No. 2≠, U.S. Patent No. 3. xot, No. 3i3, No. 3.3/7.32-, No. 3 #761.2 (i
No. 6, No. 3.761,276, No. 3.850. (
i37, 3.923.513, 4.035
．． No. 185, No. 4,395゜478, No. 4,431
, No. 730, No. 4,504.570 Yo CI -/
Ha Patent No. 0017148, Research Disclosure! 8RD16345 (November 1977)
18155 (May 1979), ll&L23510
(November 1983) and the like.

The composition of the silver halide is not particularly limited, and silver bromide, silver iodobromide, silver chloride, silver chlorobromide, silver chloroiodobromide, and the like can be used. The halogen compositions of the core and shell may be the same or different.

The silver halide preferably used in the present invention does not contain silver iodide, but even if it does contain it, it is not more than 10 mol %.

The average grain size of the silver halide grains (represented by the diameter of the same sphere as the grain) is preferably 2.0 μm or less and 0.1 μm or more, and particularly preferably 1.0 μm or less. 2μ or less O, koμ or more. Although the grain size distribution may be narrow or wide, it is preferable to use a so-called "monodisperse" silver halide emulsion with a narrow grain size distribution in order to improve graininess, sharpness, etc. in the present invention. .

Monodisperse silver halide grains in the present invention have a grain size distribution M as defined by the following formula. In other words, when the S preparation difference in the S diameter distribution is divided by the Si average grain diameter i, the value is 0.20 or less. In the case of a particle having a shape other than a cube or a sphere, the average value of the diameter of a circular image of the same area as the projected image, and the individual plate diameter. is ri″t
', and the number is i, then we can use the number 7 defined by the number below.

Σni For the above purpose, the above particle size was determined by the method of each volume commonly used in the relevant technical field.
can be measured. A typical method is "Particle Size Analysis Method JA, 8.
T, M, Symposium on Ride Microscopy, llij! fif-1 Rihiro ~/page 22, or in chapter 1 of ``Theory of Photographic Process'', co-authored by Mies and James, 3rd edition, published by Macmillan <1ytt year).

The particle size can be measured using the projected area of the particle or an approximate diameter value. In addition, in order to satisfy the target level 11 of the light-sensitive material, two or more types of monodispersed silver halide emulsions with different grain sizes or F! Plural particles of the same size but with different sensitivities can be mixed in the same layer or layered in different layers. Furthermore, polydisperse silver halide grains of Zal or higher or a combination of a monodisperse emulsion and a polydisperse emulsion can be used in combination or in a superimposed manner.

The shape of the silver halide grains of the present invention may be regular crystal shapes such as octahedral or tetradecahedral, or irregular crystal shapes such as spherical.
ar ) na Ili! It may also have an a-shape and a t-shape.

In particular, an emulsion may be used in which the total projected area of tabular grains having a length/thickness ratio of 3 or more, particularly 1 or more, accounts for 04 or more. Further, an emulsion having a composite form of these crystal forms or a mixture thereof may be used.

The halogenated emulsion used in the present invention is inside the powder! Alternatively, chemical sensitization can be carried out by sulfur or selenium sensitization, reduction sensitization, sensitization, etc., either alone or in combination.

For detailed examples, see Research Disclosure magazine/1617&≠j-fl (/7 published in February 2017)
It is in the patents described in P, 2j, etc.

The photographic emulsion used in the present invention is spectrally sensitized with a sensitizing dye represented by formula (I). Next, general formula (I) will be discussed in detail in a#4.

w', w%W, W are hydrogen atoms, halogen atoms (e.g. fluorine, chlorine, bromine, iodine), alkyl groups having a carbon number of /~/2, preferably carbon atoms (e.g. methyl, ethyl, n- buapil, lobechill, t-
butyl, n-amyl, 5ec-7 mil), carbon number/~i
t, preferably a substituted alkyl group having 1 to t carbon atoms (e.g. benzyl, 7-ralkyl such as λ-phenylethyl, λ-
Hydroxyalkyl such as human axyethyl, 3-hydroxypropyl, alkoxyalkyl such as 2-methoxyethyl, λ-ethoxyethyl, co(comethoxyethoxy)ether, trifluoromethyl, λ.

2. Halogenated alkyl 1 such as 2-trifluoroethyl, alkenylalkyl such as allyl, carboxyalkyl such as carboxymethyl, cocarboxyethyl,
Heterocyclic substituted alkyl such as furfuryl, tetrahydrofurfuryl, etc.), carbon number 1~/2, preferably carbon number /~!
Alkoxy crystal (for example, methoxy, ethoxy, i-probyloxy), having 7 to 1 carbon atoms. Preferably carbon number/~
Substituted alkoxy crystals of t (e.g. benzyloxy, λ-phenylethoxy, λ-methoxyethoxy, etc.).

2.2-trifluoroethoxy), carbon I! 6-10,
Preferably, 6 to Ir substituted or unsubstituted IJ- groups (for example, phenyl, -1naphther, p-tolyl, m-
anisyl, p-chromitzel, p-carboxyphenyl), carbon number 6-10. H"!t.

-a-oxy group (e.g., phenoxy, λ-naphthyloxy, p-tolyloxy, m-7nisyloxy, p-chlorophenoxy, p-carboxyphenoxy) , human mixi group, carboxy group, carbon number - ~ lr.

Preferably carbon! ! ! λ ~ ♂ [11-substituted or unsubstituted alkoxycarbonyl: I6 (for example, methoxycarbonyl, ethoxycarbonyl, -1methoxycarbonyl, benzyloxycarbonyl) 1 wood number ~ 1
2, preferably acyloxy having 2 to 7 carbon atoms! (?9 For example, acetyloxy, butionyloxy, benzoyloxy), carbon number λ-/2, preferably 1 (, ( means carbon 'A number 2-7
7 cylamino & (e.g. acetylamino, propionylamino, benzoylamino), carbon number λ ~ 72%, preferably λ ~ 7 acyl group (e.g. acetyl, propionyl, benzoyl), carbon number l~/λ, preferably carbon Number/~1 of substituted or unsubstituted carbamoyl groups (e.g. carbamoyl, hemethylcarbamoyl, piperidinylcarbonyl, morpholinylcarbamoyl), heterocyclic groups (e.g. -thienyl, λ-thiazolyl, -furyl) represent

Furthermore, a benzene ring may be formed by W 2 and R2, R2 and Kazu, or W 2 and W 2 .

Wl and R4 are preferably hydrogen atoms, except when forming a benzene ring. Furthermore, it is preferable that it is not formed on the benzene ring.

1 and 2 each have carbon numbers/~λO preferably/~
j is an alkyl group (eg, methyl, ethyl, n-propyl, lobethyl, t-butyl, n-amyl, 5ec-amyl) having 7 to -0 carbon atoms, preferably carbon i1! /-r
Substituted alkyl groups (e.g. -sulfoethyl, 3-sulfopropyl, ≠-sulfobutyl, sulfoalkyl such as 3-sulfobutyl, λ-(≠-sulfophenyl)ethylnatonosulfoaralkyl, carboxymethyl, λ-carboxyethyl, 3- Carboxyalkyl such as carboxypropyl, hydroxyalkyl such as -monohydroxyethyl, 3-hydroxypropyl, alkoxyalkyl such as λ-methoxyethyl, -1ethoxyethyl 1.2-(λ-methoxyethoxy)ethyl, -9λ , -trifluoroether, λ.

λ, alkyl halides such as 3.3-tetrafluoropropyl, flukanesulfonylaminoalkyl such as λ-methanesulfonylaminoeternato, alkenylalkyl such as allyl), ? L- [was.

Particularly preferred as 91 are methyl, ethyl, and 3-sulfopropyl. Further, it is particularly preferable that both of 1 and 2 are sulfoalkyl.

R3 is a hydrogen atom, and the number of carbon atoms is /~t.
substituted alkyl group (e.g. methyl, ethyl, n-propyl, befuryl, λ-7 enyl ether, λ-methoxyethyl, tolylethyl), MIA having 6 to 10 carbon atoms or mW
+6 aryl group (for example, phenyl, naphthyl, tolyl, phenyl, carboxyphenyl, chlorophenyl, thienyl, furyl), preferably a hydrogen atom, methyl, ethyl, or phenyl, and particularly preferably ethyl.

X is a charge balancing group. When it is an anion, it represents, for example, a halide ion such as chloride, bromide, or iosito, an alkyl sulfato ion such as methylsulfatolsulfate, an arylsulfonate ion such as p-toluenesulfonate sulfonate, or a perchlorate ion. If it is a cation,
Represents pyridinium, triethylammonium, sodium ion, potassium ion, hydrogen ion, etc.

In the absence of X, the compound of formula (I) -a forms an inner salt.

Type 1A [! The following are particularly preferable.

a. -1 formula (in which nI and Rt are both sulfoalkyl groups.

Furthermore, R3 in a is an ethyl group.

In the general formula], both Wl and R4 are hydrogen atoms, and Wl and R3 do not form a benzene ring t'.

b' and b are generally ethyl groups.

In C0 general formula (I), H,! , H2 are all sulfoalkyl groups, wt and w' are both hydrogen atoms, and W and W do not form on the benzene ring.

In c' and c, 几 is an ethyl group.

Next, specific examples of the sensitizing dye used in the present invention will be shown. Of course, the present invention is not limited to this.

Compound examples of general formula CI) i/ ■ −λ ! -3 ■−≠ ■ -t (C) 12) 38υ3H small (C2h5) s-2 t 1-i.

(C) 12) 3S (J3) 1 (ch2) 4su3- (to H2) 38 (J3 N a 1-// l -/- 1-/j ■-77 1-/,!' 1-/ri I -/daCM2C)42N)il:1(J2CH31-/6 eh2ch2eh2cuuh ■--/ 1-.2λ [-23 ■--μ The compound represented by the general formula (f) is silver halide 1
per mole, /X10-6 to X/0-"7k, preferably j
0-3 mok, particularly preferably IX/0-6~/
It is contained in a silver halide photographic emulsion at a ratio of X/0 to 3 moles.

The compound represented by general formula (I) may be used in combination with other useful sensitizing dyes. Preferred compounds when used in combination include general formula (I1),
Some of the things that are suggested are:

General formula (If) l-2! W5 and WS are hydrogen atom, halogen atom, and foot*, respectively.
or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, lt 1 * is unsubstituted aryl thread, #, substituted or unsubstituted aryloxy group, hydroxy group, carboxy group device 1 negative or device 1^ alkoxycarbonyl group,
It represents an acyloxy group, an acylamino group, an acyl group, a substituted or unsubstituted carbamoyl group, or a heterocyclic group.

R4 and R3 each represent a substituted or unsubstituted alkyl group, provided that one of them represents a hydroxyalkyl group, a carboxyalkyl group, or a sulfoalkyl group.

R4 represents a hydrogen atom, a substituted or unsubstituted alkyl group, IIA, or an unsubstituted aryl group.

X is a group for charge balance.

In the absence of X, the compound of general formula (II) forms an inner salt.

General formula (fi+) R drop (X) R7 and R'' each represent ff1.lA or an unsubstituted alkyl group, provided that at least one of them represents a hydroxyalkyl group, a carboxyalkyl group, or a sulfoalkyl group.

R9 represents a hydrogen atom, a substituted or unsubstituted alkyl group, 210 or an unsubstituted aryl group, or a negatively charged ketomethylene residue forming a holopolar cyanine dye.

X is a charge balancing group.

When X is absent, the compound of general formula (Iff) forms an inner salt.

Next, the general formula [■] will be explained in detail.

WS, W& are each hydrogen atom, halogen atom (e.g. fluorine, chlorine, bromine, iodine), carbon number 1-12, preferably carbon number 1-5 °? Rukyl group, carbon number 1-18,
Preferably a substituted alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, preferably 1 to 5 carbon atoms, a substituted alkoxy group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms, and a substituted alkoxy group having 1 to 18 carbon atoms, preferably having 1 to 8 carbon atoms. R1 having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms
Monosubstituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms,
Hydroxy group, carboxy group, substituted or unsubstituted alkoxycarbonyl group having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms, acyloxy group having 2 to 12 carbon atoms, preferably 2 to 7 carbon atoms, 2 to 7 carbon atoms 12, preferably 2 to 2 carbon atoms
7 acylamino group, carbon number 2 to 12, preferably 2 to
7 acyl group, having 1 to 12 carbon atoms, preferably 1 to 12 carbon atoms
8 substituted or unsubstituted carbamoyl group, hetero I! 2 groups (e.g. 2-thienyl, 2-thiazolyl, 2-furyl)
represents.

R4 and R1 each have 1 to 20 carbon atoms, preferably 1
-5 alkyl group, carbon vIt -20, preferably a substituted alkyl group having 1 to 8 carbon atoms.

R- represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, preferably a hydrogen atom, a methyl group, an ethyl group, or a phenyl group; Particularly preferred is ethyl group.

X is a charge balancing group. When it is an anion, for example, halide ions such as chloride, bromide, iosito, alkyl sulfate ions such as methyl sulfate and ethyl sulfate, p-toluenesulfonate,
It represents an arylsulfonate ion such as p-chlorophenylsulfonate, a perchlorate ion, etc. When it is a cation, it represents pyridinium, triethylammonium, sodium ion, potassium ion, hydrogen ion, etc.

When X is absent, the compound of general formula [■] forms an inner salt.

Next, general formula (III) will be explained in detail.

R7 and R1 are each an alkyl group having 1 to 20 carbon atoms, preferably 1 to 5 carbon atoms; a substituted alkyl group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms; tolu group (e.g. 2-sulfoethyl, 3-sulfopropyl, Sulfoalkyl such as 4-sulfobutyl, 3-sulfobdel group, sulfoaralkyl such as 2-(4-sulfophenyl)ethyl, carboxyalkyl such as carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 2-hydroxyethyl, 3 −
Hydroxyalkyl such as hydroxypropyl, alkoxyalkyl such as 2-methoxyethyl, 2-ethoxyethyl, 2-(2-methoxyethoxy)ethyl, 2,2
．． 2-trifluoroethyl, halogenated alkyl such as 2,2,3.3-tetrafluoropropyl, alkanesulfonylaminoalkyl such as 2-methanesulfonylaminoethyl, alkenylalkyl such as allyl).

R droplet is a hydrogen atom or a substituted one having 1 to 8 carbon atoms or no 'I
an alkyl group having 6 to 10 carbon atoms, a substituted or unsubstituted aryl group, or (where Z represents an oxygen atom or a sulfur atom, R''
%R" represents an alkyl group having 6 or less carbon atoms, a substituted alkyl group having 6 or less carbon atoms (yxmm represents a chlorine atom, a fluorine atom, a phenyl group, etc.) or an alkoxy group having 1 to 4 carbon atoms. , a hydrogen atom, a methyl group, an ethyl group, and a phenyl group are preferred, and an ethyl group is particularly preferred.

X is a charge balancing group. When it is an anion, for example, halide ions such as chloride, bromide, iosito, alkyl sulfate ions such as methyl sulfate and ethyl sulfate, P-toluenesulfonate,
It represents an arylsulfonate ion such as p-chlorophenylsulfonate, a perchlorate ion, etc. When it is a cation, it represents pyridinium, triethylammonium, sodium ion, potassium ion, hydrogen ion, etc.

In the absence of X, the compound of general formula (III) forms an inner salt.

Next, specific examples of compounds represented by the general formulas (1) and (Ill) will be shown.

Compound example of general formula (II) 1 -t ■-6 [-7 ■-2 ■-≠ ■-? ■-2 ■-10 Examples of compounds of general formula (I) ■-Hiroshi ■-2 (Ckiz ) s 8L) 3 to a t-t C2)1゜11-J C2)18 Found in general formula (I) The compound that can be grown is Mataru D/764
It may also be used in combination with other cyanine dyes, merocyanine dyes, double merocyanine dyes, etc. described in 13 (/1973, February) ■.

When the sensitizing dye represented by (n) and/or H (ill) above is used in combination with (I), the molar ratio is θ to (I).
It is preferable to use the range of 2 to 2.

The sensitizing dye used in the present invention can be directly dispersed into the emulsion. In addition, these are first dissolved in a suitable solvent such as PJ, alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixed solvent thereof, and then added to the emulsion in the form of a solution. You can also. Ultrasonic waves can also be used for dissolution. The method of adding this sensitizing dye is [JS-j
, 444, 27, etc., a method and time of dissolving a dye in a volatile organic solvent, dispersing the solution in a hydrophilic comoid, and adding this dispersion to an emulsion. Min l18≠6--≠lr! A method of dispersing a water-insoluble dye in a water-bathable solvent without dissolving it and cooling the dispersion into a total emulsion as described in US-J, 1.
rkoλ, 13! Surfactant static liquid ice base km? '4L, Method 2 of adding the solution into an emulsion, as described in JP-A-57-7≠62≠. : The method described in JP-A No. 26, Shoto-tor, No. 26, in which a dye is dissolved in a substantially water-free acid and the solution is poured into an emulsion as a foil layer, is used. Other additions to emulsions include U.S. Patent No. 2. Ri/ko, 3≠3 issue, Fl
@j, 317-2, 60! No. 2.226.
No. 227, same No. 3. The method described in IAλ, No. 133, etc., can also be used. 19 The above sensitizing dye #: may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but of course may not be dispersed during any step in the preparation of the halogen north emulsion. Can be done.

The photographic emulsion used in the present invention contains be/zene sulfur 7CIIm, thiocarbonyl compound, etc. for the purpose of preventing fogging during the manufacturing process, storage, or photographic processing of the light-sensitive material, or stabilizing photographic fins. be able to.

For more detailed examples of antifoggants or stabilizers and their uses, see, for example, U.S. Pat.
ta, a74c, itg3.21λ, rihiro 7,
Special Public Shoj No. 2161.0, Research Disclosure (fil)) Magazine 176 Hiroj (I5'71'4/2
``Stabilization of silver halide photographic emulsions'' by M.A.''ViM and E. J. Birr.
ation of PhotographicSilv
er)ialide Emulsions) 7 Ocal Press (Focal Press), published in 1998, etc.

In the present invention, rI! A variety of color couplers can be used to form a positive color image IJl. A color coupler is a compound that generates a substantially non-diffusible dye by a coupling reaction with an oxidized product of an aromatic primary amine color developer, and releases a substantially non-diffusible dye. Preferred are compounds that are non-diffusible in nature. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolones or pyrazoloazole compounds, and open-chain or heterocyclic metatomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in [Research Disc A-Jar] /16/744431/271/2
Monthly issue) P, 2j, VII-D section, +=r7g6/r7
/7(/P7P'lE//Month issue>5pxv*mmt/
-321Ajp- and the compounds cited therein and described in -am.

Ninth colored coupler that corrects unnecessary absorption in the short wavelength range of the generated dye, coloring dye with appropriate diffusivity? Colorless couplers, L)l couplers that release a development inhibitor upon coupling reaction, and polymerized couplers can also be used.

As the binder or preservative colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

In the light-sensitive material of the present invention, a color capri-preventing agent or a color-mixing preventive agent can be used.

A representative example of these is JP-A-62-2/! No. 272 600~
One person is listed on page 63.

Various anti-fading agents can be used in the light-sensitive material of the present invention.

Representative examples of these anti-fading agents are disclosed in JP-A-1H2-2/J
No. 272, page 4cooNp4to.

The photosensitive material of the present invention includes dyes that prevent irradiation and halation, ultraviolet absorbers, reversible agents, optical brighteners, matting agents, air fog preventive agents, coating aids, hardeners, #
! #S can be added with an antistatic agent, slippery improver, etc. Representative examples of these foil additives are listed in Research Disclosure Magazine/16/7644JVI ~
P7. Published in R year/J month) p2! ~core, and 1′!
711t716 (Issue 711/July) p6≠7~6
It is described in 1/.

The photosensitive material according to the present invention includes, in addition to the halogenated rice emulsion layer,
It is preferable to appropriately provide auxiliary layers such as a film holding layer, intermediate IL filter j@, antihalation agent, backing layer, and white reflection layer 1-.

Regarding the photographic emulsion layer and other layers in the photographic light-sensitive material of the present invention, Search Disclosure Magazine/I6/7.64! j
Items listed in Section XV// (published in /?7J'fl-/J) P2♂ and European patents 0. /12.2!3 issue and Tokukai Showa 6 Fuita 71I! ! It is coated on the support described in No.

Also research disc a-jar magazine A6/7tlAJ
Section XV Pat to Jl: The coating method described can be used.

The present invention can be applied to a wide variety of color photographic materials.

For example, typical examples include color reversal film for slides or television, color reversal paper, and instant color film. It can also be used for full-color copying machines and color hard copies for storing CWT drawings. The present invention is the following, 1 Research Disclosure” Magazine/7/Co3 (
It can also be applied to black-and-white light-sensitive materials that use all three-color coupler mixtures, such as those described in J.D.

The photosensitive material of the invention can be applied to a secondary color diffusion transfer material. Attached to the spot are 1 Research Day Closure magazine/%1si6a<i176), I￥f Gansho t.
pi-, 2s ri 3J6, +51 A j-23≠ri 1
The compounds and methods described in the above may be used in combination.

Historically uninvented can also be applied to black and white photographic materials.

Examples of black and white (B/W) photographic materials to which the present invention can be applied include JP-A Shojter λorzpo, JP-A ShotoO-, 21>
There are B/W@contact photosensitive materials described in 0032, such as Vix ray photosensitive materials, duplex photosensitive materials, micro photosensitive materials, XM1 photosensitive materials, and printing photosensitive materials.

After imagewise exposure, the uninvented direct positive photographic light-sensitive material is subjected to fogging treatment as shown in ().

As mentioned above, the fogging process can be carried out either by exposing the entire surface of the photosensitive layer, called the so-called "original fogging method", or by developing it in the presence of a nucleating agent, called the "chemical fogging method". t may be used. Development may be carried out in the presence of a nucleating agent and a fogging agent. Also, the light-sensitive material containing all the nucleating agent may be exposed to light.

In the present invention, it is particularly preferable to carry out fogging treatment using a nucleating agent.

The entire surface kiln, that is, the fog kiln in the one-party fogging method of the present invention, is performed after imagewise exposure, and the development process and the 71st step are performed during the development process. The imagewise exposed light-sensitive material is immersed in a developer solution or a pre-bath of the developer solution, or is taken out from the solution and exposed in an exposure tube before drying, but it is most preferable to expose the material in a developer solution.

As the light source for the fog f4 source, a light source within the sensitivity wavelength of the photosensitive material may be used, and generally any of fluorescent lamps, tungsten lamps, xenon lamps, sunlight, etc. can be used. These specific ten thousand @ are, for example, British patent 1.131
．． ．． No. 343, Tokko Akira≠! -/No. 2710, same≠3-/
No. 2702, same! Zaichi No. 6236, Tokukai Sho ≠ wo 1272
No. 7, same! A - / j 7J jO No., lq j 7
-/λ Rihiro No. 31r, Fl jg-62612, 1
lffLtzaichi 1s073F, same j♂-70223 (corresponding US patent 11≠, Hirohiro O9♂!/No.), same 5r-i
It is described in λQλhiro No. 1, etc.

As the nucleating agent used in the present invention, all of the following compounds developed for the purpose of nucleating σ and inner layer type bald/silver oxide can be used. Nucleating agents may be used in combination of more than one type of nucleating agent. To explain in detail, nucleating agents include, for example, [Research Disclosure J].
closure) g, AJJj"3≠ (lli♂3 years/monthly issue) J"0-74L Sada, same magazine, /16/! /lλ(/
Published in July 1976) 1976-77, and the same magazine, /16
233-70 (Published in March 2013) 3416-33
There are compounds listed on page 2, and these include quaternary heterocyclic compounds (hereinafter referred to as (N-1)), hydrazine compounds (
(hereinafter referred to as (N-u)) and other compounds.

Examples of the above [He-Star] are listed below.

(N-1-/) j-ethoxy-λ-methyl-/-propargylquinolinium bromide (N-1-2) 2. +-dimethyl-7-propargylquinolinium promide (N-1-J) 2-methyl-/-(3-[λ-(≠
-methylphenyl) hydrazonocobutyl 1 quinolinium yosito (he-1-1) J, Hiro-dimetherodihyde O pyrido [λ, /-b) benzothiazolium bromide (N-1-j) 4-ethoxythiol Luponylamino-comethyl-/-buOpargylquinolinium triple oromethanesulfonate (N-1-A) 2-methyl-6-(3-phenylthioureido)-t-propargylquinolinium bromide (N-1- 7) A-(j-benzotriazolecarboxamide)-11methyl-7-propalkylquinolium trifluoromethanesulfonate (N-[-f) 6-(j-(2-mercaptoethyl)waleido]---methyl - 1-10,e rugylquinolinium trifluoromethanesulfonate (N-1-2) b-13-C3-(!t-mercapto/, 3.1I--theadiazole-coyltheo)buavir] ureido)-2-methyl-7-propargylquinolinium trifluoromethanesulfonate (Nl-10) j-(J-mercaptotetrazol-/-yl)-11methyl-7-propargylquinolinium iodide (N- Specific examples of n) are shown below.

(N-■-/) /-formyl-(≠-[3-(
,2-methoxyphenyl)waleido]phenyl)hydrazine(N-■-co] l-formyl-2-1≠-[3-(J
-(J-(λ,≠-di-tert-pentylphenoxy)propyl]walate)phenylsulfonylamino]phenyl)hydrazineC,N-n-3> /-formylluco-(≠, [3-
(yo-mercaptotetrazol-/-yl)benzamido]phenyl)hydrazine (N-11-1) /-yt<Lumilou J-(44-
(j-[J-(j-mercaptotetrazol-7-yl)phenylthureido)phenyl]hydrazine(her-■-ri/-formyl-[Hiro-(3-(N-(
r-Mercaptodermethyl-/, 2,44-triazol-3-yl)carbamoyl)butapanamido)phenyl]hydrazine (N-11-A)/-formylluco-(≠-[3-1-
(Hiro-(3-mercapto-1/, J, ≠-triazole-≠ monoyl) phenylcarbamoyl) bu-panamide] phenyl) hydrazine (he-11-7) /-formyl-λ-[≠-13-
[He-(j-Mercapto-/.

3. Hiro-theadiazole-coyl)carbasoyl]balamide)phenyl]-hydrazine (N-n-r) 2-C≠-benzotriazole-!
-Rupoxamide)fer] 1/-Formylhydrazine(he-■-ta) 2-[μ-(J-(N-(benzotriazole-y-carboxamide)carbamoyl]propanamido)phenyl)-/-Formylhydrazine( to -■-10)/-formyl-2-(Hiro-[/-(N
-Phenylcarbamoyl) Thiosemicarbamide [Phenyl] Hydrazine Other hydrazine-based nucleating agents include, for example, JP-A-Sho No. 7461λ, Mokukuni Patent No. ≠,! 6o, b3 issue, 44th issue, '471, 2uff issue, and even 2nd issue.
, jla3.7Irj and the same, ! -11.

It is written in the 2t issue.

The nucleating agent can be contained in the sensitive material or in the processing solution for the sensitive material, preferably in the sensitive material.

When the nucleating agent is incorporated into the sensitive material, it is preferable to cool it to the latent type/%O silver saponide emulsion layer, but the nucleating agent may diffuse into the silver halide layer during coating or processing. Other ingredients 1-9 may be added to the intermediate r-1 subbing layer or pack 1- to the extent that they do. When a nucleating agent is added to the processing solution, the developer bath may be contained in a low pH prebath as described in JP-A-771310.

When the nucleating agent is contained in the sensitive material, the amount used is preferably 10-8 to 10-2 mol per 1 mol of iron halide.
More preferably, the amount is 10-7 to 10-3 mol.

In addition, when a nucleating agent is added to the treatment solution, the amount used is preferably 12 io ~/Q mol,
More preferably it is io -io moles.

A nucleating agent with fc of 28 or higher may be used in combination.

In the present invention, in order to further promote the action of the nucleating agent, the following nucleating agents can be used.

Nucleation accelerators include tetrazaindenes, triazaindenes, intazaindenes, and mercapto groups optionally containing at least 7 M mercapto groups which may be INj-converted with an alkali metal atom or an ammonium group. 6λ-
/Hirojri 3-11! (iz ~ 30 pages), Tokugan Shobuichi -
l≠! P33 (1 to 11 members) The compound described in K can be added.

Currently 1! Solution II is preferably mg of alkaline water containing an aromatic primary aban color developing agent as a product.

Aminophenol compounds are also used as color developing crude drugs, but p-phenylenediamine compounds are preferably used, and a typical example is 3-methyl-≠
-Amino-N-N, diethylaniline, 3-methyl-Hiro-aminoh-ethyl-to-ββ-humanmixietheraniline 3-methyl-Hiro-aminoh-ethyl-to-β-
Methanesulfonamide etheraniline, 3-methyl-≠
-aminohether-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. These compounds can be used in combination in amounts of 2'1jIA or more depending on the purpose.

The pH of these color developing solutions is from 2 to 12, preferably from j to /1. ! It is.

After color development, the photographic emulsion/llll1 is usually subjected to a bleaching process.

The bleaching process may be carried out simultaneously with the fixing process.
! 4 white fixing process) may be performed separately. In order to speed up the processing, it is also possible to use a processing method in which the product is bleached and then processed on a later date.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The rinsing water t in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used, such as couplers), the usage, the history of the rinsing water, the rinsing water temperature, the number of rinsing stages, the irradiation method such as same flow, forward flow, etc. It can be set in a wide range depending on other extreme conditions.

The halogenated color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to obtain an internal relationship, it is preferable to use each Keyaki precursor of a color developing agent.

On the other hand, various known developers can be used to develop the black and white photosensitive material of the present invention. That is, polyhuman mixybenzenes, such as hydroquinone,
- Arohydroquinone, λ-methylhydroquinone, catechol, pyrogallol, etc.; aminophenols, such as p-aminophenol, N-methyl-p-aminophenol, 2. ≠-diaminophenol, etc.; 3
- biracilinds, such as /-phenyl-3-pyrazolidones, l-phenyl-≠l≠'-dimethyl-3-pyrazolidone, l-phenyl-≠-methyl-≠-hydroxymethyl-3-pyrazolidone, j.

J-dimethyl-l-phenyl-3-pyrazolidone, ascorbic acids, etc. can be used alone or in combination. Further, the developer described in JP-A-5R-SR-21 can also be used.

For detailed examples of developers, preservatives, buffers, and discipline methods for black-and-white photosensitive materials, see [
It is described in "Research Disclosure" magazine, 76≠j (published in January 1971), sections XIX to XXI, etc.

(Example) The present invention will be described in detail below with reference to Examples, but the present invention is not limited thereto.

Example 1 An aqueous solution of potassium bromide and silver nitrate made from vI4 of Emulsion A-/ was prepared at 3 o per mole of Ag.
g-3. ≠-dimethyl-7,3-thiazoline-theone and lead acetate and entangled at the same time, and the average particle size is approximately o, y, oμ
A monodisperse silver bromide emulsion of m-octahedrons was obtained. 1 plane to this emulsion
6 Mf of sodium thiosulfate and 7 Mf of gold chloride per mole
9 (≠ water salt) and heated at 75°C for 10 minutes to perform chemical sensitization treatment. The thus obtained 7'cJA silver grain core was further grown in the same precipitation environment as the first time to obtain a monodisperse core/shell bromide emulsion with an average grain size of 0.7 μm and an A-hedron. . The coefficient of variation in particle size was approximately 10 inches.

To this emulsion were added 189 sodium thiosulfate and i, zq of chloroauric acid (≠ hydrate) per mole of silver at 60°C.
Chemical sensitization treatment was carried out by heating for a minute to form an internal m-image type saponified emulsion A-/k#.

Sample 10 of a multilayer color light-sensitive material having the layer structure shown below was prepared using the above-mentioned emulsion on a paper support laminated on both sides with polyethylene.

(Layer structure) The composition of each layer is shown below. The numbers indicate the amount of coating applied to the seams. The coating amount of the silver halide emulsion and commoid silver ij is expressed as 2, and the sensitizing dye is expressed as the addition amount t mol per mol of silver halide.

Support polyethylene laminate paper [Secondly, a white pigment (Ti(3
2) and Yoimi dye (group 1-containing) No. E/7m silver halide emulsion Q,, 2.4 min n)
*m color t, C, m-7) 2. Oxlo-5 Spectral Sensitized Color Collection (II-#/) 2.0X10-4 Gelatin I, II Cyan Cuffler (
ExCC-/) 0.2/Cyan coupler (ExCe
-2) 0.26 ultraviolet absorber (ExLIV-/)
0.17 Cancer agent (Exa-/) 0.
3 Current regulator (ExGC-/) 0.02 Stabilizer (BxA-/) 0.001° Nucleation accelerator (ExZ8-/)J, 0x10-' Nucleating agent
(ExZK-/)f, 0x10-'th w2tm Gelatin 1. Reference/color mixing inhibitor (ExKB-/) Solvent (Ext-'/) Solvent (ExS-2) 83rd layer silver halide emulsion public sensitizing dye (ExSS-J) J Gelate/Magenta coupler (ExMC-/Color Image stabilizer (Ex8A-/) Solvent (ExS-j) Current gR regulator (ExGC-/) Stabilizer (BxA-/) Nucleation accelerator (ExZ8-/)2 Nucleating agent (ExZK-/)/ E≠layer gelatin color mixing inhibitor solvent solvent 83rd layer (ExKB-/) (ExS-/) (Exa-co) Q, θri O, / 0 0.10 O, -3, OX / 0''-' / ,0ri0./6 0,.20 0.2!0.02 o,oot ,7X10-4 .4'X1O-5 0,≠7 0.03 0.03 0.03 Colloidal silver 0.02 Gelatin O,4A color mixture prevention agent (Ex
KB-/) 0.0! Solvent (ExeS-/
) 0. OJ row plot (ExS-J)
0.03 E6th layer Same as Ehiro layer E71-/10 gun emulsion 0-ri Q spectroscopy pI
I-sensitive dye (k, xsb-J) 41. λ×IO-'gelatin -, /7 (Eng.
,2) 0.20 solvent (Ex8−≠)
o, -〇Development regulator (Ex(jc-/) 0
．． OA stabilizer (ExA-/) 0.00/
& Nuclear Promotion JIIH) (ExZ8-1)! ,0X10-
'Nucleating agent (kxZK-/)/, JXlo-'
-t rf4 Ceratene O0j Hiro ultraviolet absorber (ExυV-,2) 0.21 solvent
(Exa-44) 0.01r E-layer gelatin/acrylic modified copolymer of -t polyvinyl alcohol (degree of modification/7fb) 0. /7 Liquid paraffin 0.0! Latex particles of polymethyl methacrylate (average particle size λ, t μm) o, oz 100 H/layer gelatin! In addition to the above composition, gelatin hardening agent Ex (jK-
/ and surfactant t- added.

Good compounds used to prepare samples: (ExCC-/) Cyan coupler (ExYC-/) Yellow coupler (MxCC-λ) Cyan coupler (Ex88-J) Spectral sensitizing dye (kJxMC-/) Magenta coupler (Ex88) -4t) Public party extrag color T-(Exa-4
t) Solvent (ExUV-/) Ultraviolet absorber 5 (J3- (ExS-/) Solvent (Exa-2) Solvent (Exa-J) Solvent l mixture (volume ratio) (I): t2): (3) ( ExGC-
/) Current regulator z:r: ta mixture (weight ratio) (ExUV-J) Ultraviolet absorber above (lji (2):
Weight ratio) (ExSA-/) Color image stabilizer (ExKH-/) Color mixing inhibitor 0)i (ExA-/) Stabilizer≠-hydroxy-j, A-1-rimethylene-/.

J, 3a, 7-sontrazaindene (hxZ8-/) nucleation promoter λ-(3-dimethylaminopropylteo)-! -Mercapto i, 3. Formation of q-thiadiazole hydrochloride (ExZK-/) 6-nitoxythiocarponylamino-methyl-1-
Propargyl quinolinium trifluoromethanesulfonate (ExGK-/) gelatin hardener l-oxy-3,5-dichloro-8-triazine sodium salt In sample 101, the spectral sensitizing dye of No. EIJil was changed as shown in Table 1. Samples 102-10
Set it to 6.

Next, sample 107 is obtained by changing the nucleating agent to N-Ir-6 in sample 102.

The color light-sensitive material thus prepared was subjected to wedge exposure (7710 seconds, 10OC100C) and then subjected to the following processing steps 87.

Processing process Time Temperature “Liquid”’ Refill volume −
Ryo color development 13! Sand 3rc itbu 300d/r
r? Bleach constant 4 ≠Osho 33℃ 31. 300w
dl/n? Water washing (I) Hiroo second 33℃ 31 water washing (2111-0 33℃ lit J20td/
rr? The washing water supplementation method supplements the washing bath (2) with light and guides the overflow liquid of the washing bath (2) to the washing bath f1).
The so-called same-current supplementary light method was used. At this time, the amount of bleach-fixing liquid brought into the washing bath (I) from the dimpled foot bath (I) due to the photosensitive material is 3j4/a, and the magnification of the water washing water sleeve light-reducing liquid to the waiting amount of bleach-fixing liquid is 1. It was double that.

The composition of each treatment solution is as follows.

Color-forming liquid ethylene diamine trachysmethylene phosphonic acid diethylene glycol benzyl alcohol potassium bromide sodium sulfite to bis(carboxymethyl)hydrazine triethanolamine 8-ethyl-(β-methanesulfonamidoethyl)-3-methyl- Hiro-aminoaniline sulfate potassium carbonate optical brightener (diami/ /,!y/υa/2.Om/, 601-, Hiro≠, OP haj1p 0d/41', Hirodi, op λ, ri 2 Hiroshi, ry 6.011 7. λri A, ni # 7. Kota 30.0? 2. Evening, oy /, 011 /, conostilbene series) ammonium nitrate io, op p) i (at'c) bleached feet 10 liquids! 0 //, 0θ Ethylenediamine ≠ Acetic acid, Cona triwaum, λ hydrate Ethylenediamine ≠ Acetic acid, upper'e (m ), Ammonium cohydrate Ammonium thiosulfate (7oop/Jip- Sodium toluenesulfinate Sodium bisulfite 2- Amino-mercapto-/, 3゜≠-thiadiazole≠, Ota same as mother liquor 70, (Nl /rOml ao, oy coo, oy 0, trip) i(,2j'C) l,,, 20 Washing water Mother solution and replenisher both tap water yh type strong acid cation exchange! 11L resin (Rohm and Haas Amberlite IkL-/, 20 to 3)
and 0) i-type anion exchange resin (Amberlite 1R)
-≠oo) Water is passed through a mixed bed column filled with 2 light to reduce the concentration of calcium and magnesium ions to less than 3~/L, and then sodium incyasulate dichloride λOki/I
Next, add t and sodium sulfate/, j11/ILk. This liquid p)1t14. It was in the range of j to 7°j.

The cyan coloration of the obtained direct positive image K k (til
The results are shown in Table 2.

The Dmax i) min comma shown in the second exposure is determined as follows. In other words, on the horizontal axis,
Exposure versus I! When the degree of cyan color development is displayed on the vertical axis, it is %/1! A characteristic curve can be obtained.

The degree of cyan color development in the unexposed area is 1) max, and the cyan color development in the area where the exposure amount is sufficient is Il! l1ll f D
min, cyan coloring 112 is Dmin+(L)ma
x-Dmin)/J, on the characteristic curve,
When a tangent line t is drawn, the positive and negative signs of the slope of the tangent line are reversed and the next line becomes a comma.

This comma is an index representing the degree of hardness or softness of gradation.

In sample IQ-~107 contained in the compound *' of the present invention,
It is possible to reduce the minimum image a degree (Dmin)'i while keeping the maximum image density (I) ma
, the comma is large and sharp, giving favorable results.

[Effects of the present invention]

ri! of the present invention! By forming an image using a contact photosensitive material, a high maximum image density and a low minimum image density can be achieved.
y1 degree, and a direct positive image with high contrast and suitable for practical use can be obtained.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing a characteristic curve of a positive image obtained by the present invention. Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment

Claims (1)

[Scope of Claims] A photographic light-sensitive material having at least one emulsion layer containing internal latent image type silver halide grains which have not been fogged in advance, at least one of the emulsion layers having the following general formula [I
A direct positive photographic light-sensitive material comprising at least one sensitizing dye represented by the following. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(X) Y represents a sulfur atom or a selenium atom. W^1, W^2, W^3, and W^4 are hydrogen atoms, respectively.
Halogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, hydroxy group, carboxy group, substituted or unsubstituted alkoxycarbonyl group, acyloxy group, acylamino group, acyl group,
Represents a substituted or unsubstituted carbamoyl group or heterocyclic group. Also W^1 and W^2, W^2 and W^3, W^3 and W^
4 may each form a benzene ring. R^1 and R^2 each represent a substituted or unsubstituted alkyl group. However, at least one of them represents a hydroxyalkyl group, a carboxyalkyl group, or a sulfoalkyl group. R^3 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. X is a group for charge balance. When X is absent, the compound of general formula [I] forms an inner salt.