JPH0325435A - Image forming method for medical treatment - Google Patents

Abstract

PURPOSE:To obtain an image having high diagnostic ability output with a computer by projecting a negative image for medical treatment on the screen of a cathode-ray tube (CRT) and photographing the image with a direct reversal photosensitive material. CONSTITUTION:A negative image, that is, an image having a light area to be observed against a dark background is projected on the CRT and photographed with a direct reversal photosensitive material reproducing the image as it is. The image on the CRT is mad free from flares and the edge of the image is blackened because the outside of the screen of the CRT blackened even when it is not expected. An image having high diagnostic ability output by a computer is obtd. Especially when plural images are photographed with a single sheet, images having the high diagnostic ability are obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method of forming medical images outputted from a computer.

(Background of the Invention) With the rapid development of computers, methods for processing and outputting medical diagnostic images by computer have come into widespread use.

Conventionally, CR is the method of computer output.
A method has been adopted in which a medical image is projected onto a T (cathode ray tube) and the image is photographed on a negative/positive responsive photosensitive material. By the way, conventional medical images are
The image is presented for observation in the form of an image in which the part to be observed is bright and the background is dark (in the present invention, this image is referred to as a negative image).

Therefore, in order to photograph and observe a photosensitive material of negative/positive response type, the part to be observed is dark on the CRT.
An image with a bright background (in this invention, this is called a bright image)
must be output.

However, with this method, there is a problem in that the dark areas, which are important information points on the CRT, are spoiled by the flare of the bright areas, which are the background. Furthermore, since the outside of the CRT screen is not exposed to light, the edges of the image become blank, which obstructs diagnosis when making a diagnosis on a Jerkaste.

(Problem of the Invention) An object of the present invention is to provide a computer output image forming method with high diagnostic ability.

(Means for Solving the Problems) The problems of the present invention have been achieved by a medical image forming method characterized by projecting a medical blemish image on a CRT screen and directly photographing it on a reversal photosensitive material. .

According to this method, a negative image, that is, an image where the part to be observed is bright and the background is dark, is projected on the CRT, and the image is taken on a direct reversal photosensitive material that reproduces this image as it is (has a blurry response). There is no flare in the image, and the outside of the CRT screen becomes black even when not exposed, resulting in a black border around the edges of the image, especially when taking multiple images on one sheet. Images with high diagnostic ability can be obtained. In the present invention, it is preferable to use an internal latent image type halogenated emulsion which has not been clouded in advance as the direct reversal light-sensitive material. This is because this emulsion has higher sensitivity than other direct inversion silver halide emulsions, so there is no need to increase the brightness of the CRT screen or to extend the photographing time.

Further, as a medical photosensitive material, it is preferable for the sheet size of the photosensitive material to be 200 cm or more from the viewpoint of handling, since images are basically interpreted visually on a Scherkasten.

More specifically, a photosensitive material having on a support at least one photographic emulsion layer containing internal latent image type halogenated radical particles which are not fogged in advance is subjected to image-wise haze light and developed to directly form a positive image. In the method, the photographic emulsion layer or other hydrophilic colloid layer contains a nucleating agent and a sensitizing dye represented by the following general formula (1), and the development process is performed in the presence of the nucleating agent. A direct positive image forming method with features is preferred.

General formula (+)? In the formula, Z, 1 and z12 may be 1- or different and represent a 5- or 6-membered nitrogen-containing pseudoro ring nucleating atom group, and I11 represents 0 or 1.

R, 1 and "I2" may be the same or different and represent an optionally substituted alkyl group or alkenyl group having a total carbon number of 10 or less.

R and R+5 represent hydrogen atoms. In addition, R13 is linked to 13 R and RIs is linked to R1■ to form a 5- or 6-membered ring 1
1 may have the form:

R14 is a hydrogen atom or a lower alkyl group (which may be substituted; for example, a methyl group, an ethyl group, a probyl group, a methoxyethyl group, a phenethyl group, etc.);

More preferably, O represents an alkyl group having 5 or less carbon atoms) X11 represents an acid anion residue.

m11 represents 0 or 1, and is 0 in the case of an inner salt. '' Here, the ``nucleating agent'' is a substance that functions to directly form a positive image by acting upon surface development of an internal latent image type halogenated emulsion that has not been fogged in advance.

In addition, the term "nucleation accelerator" refers to the term "nucleation accelerator", which has virtually no nucleating ability as described above, but which promotes the action of the nucleating agent to directly increase the maximum blurring of a positive image and/or to It is a substance that acts to speed up the development time required to obtain direct positive image density.

As the nucleating agent that can be used in the present invention, all compounds conventionally developed for the purpose of nucleating latent silver halide can be used. Nucleating agents may be used in combination of two or more PJs. To explain in more detail, as a nucleating agent, for example, "Research Disclosure J"
ch Disclosurs) magazine 422,534 (1
(Published in January 1983, pp. 50-54), and these are broadly classified into three categories: hydrazine compounds, quaternary heterocyclic compounds, and other compounds.

First, examples of hydrazine compounds include the aforementioned Research Disclosure magazine A15, 162 (published in November 1976, pp. 76-77) and the same magazine Todoroki 23,510 (
Examples include those described in ``Published November 1983, pp. 346-352''.

Furthermore, specific examples include those described in the following Patent Declaration. First, as an example of a hydrazine-based nucleating agent having a silver oxide adsorption group, for example, U.S. Pat.
3 0,9 2 5, same No. 4,080,207,
Same No. 4,03 1,1 2 7, Same No. 3.718,
No. 470, P! *4,2 6 9,9 2 9, same offense No. 4,276,364, I'fj*4,2 7 8,7
4 No. 8, No. 4,385,108, No. 4,4
5 9, 3 4 7, British Patent No. 2.011,391
B, JP-A-54-74,729, JP-A No. 55-163.
No. 533, No. 155-74, 536, and No. 60
-179, '734 and others.

Other hydrazine-based nucleating agents include, for example, JP-A No. 5
No. 7-86,829, U.S. Patent No. 4,560,6
No. 38, No. 4,478, and No. 2,563,7
Examples include the compounds described in No. 85 and l'i512,588,982.

Next, examples of quaternary heterocyclic compounds include the above-mentioned Research Disclosure Magazine A22,534 and Japanese Patent Publication No. 4
9-3 8, 1 6 4, giant i52-19, 4
No. 52, No. 52-47, 326, JP-A No. 52-47, 326, JP-A No. 52-
6 No. 9,613, I'ij No. 52-3,426, I\
1. ! No. 55-138,742, Sono 60-11,837
No. 4,306,016, and Research Disclosure A23,213 (1983).
(Published in August, pp. 267-270).

Nucleating agents useful in the present invention preferably have the general formula (N
-r) or [:N-II].

General formula (N-1.) In the formula, Z1 represents a group of nonmetallic atoms necessary to form a 5- to 6-membered heterocycle.An aromatic ring or a heterocycle is further fused to this heterocycle. R1 is an aliphatic group,
X is =C1 or -N-.

I1Q represents a nonmetallic atomic group necessary to form a 4- to 12-membered non-aromatic hydrocarbon ring or a non-aromatic halogen ring. However, among the substituents of R1, z + and the substituents of Q,
At least one contains an alkynyl group.

Furthermore, one of R1, z1, and Q may have an adsorption promoting group to silver halide, Y is a counter ion for charge balance, and n is snow. This is the number of k required to balance the load.

To explain in more detail the nucleating agent represented by the general formula (N-1:l), the heterocycle completed by Z1 is, for example, quinolinium, penzimidazolium, pyridium,
Examples include thiazolium, selenazolium, imigzolium, tetrazolium, indolenium, virolinium, phenanthridinium, inquinolinium, and naphthoseridium nuclei. z1 may be substituted with a substituent, and examples of the substituent include an alkyl group, an alkenyl group,
Aralkyl group, aryl group, alkynyl group, hydroxy group, alkoxy group, aryloxy group, halogen atom,
Amino group, alkyl group, arylthio group, acyloxy group, acylamino group, sulfonyl group, sulfonyloxy group, sulfonylamino group, carboxyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group, cyano group, ureido group, urethane group, Examples include carbonate ester group, hydrazine group, hydra/n group, and imino group. As the substituent for Z1, for example, at least one substituent is selected from the above-mentioned substituents, but if two substituents are present, they may be the same or different. It is also attractive that the it' daughter group is further substituted with these substituents.

Further, as the converting group of z1, a dioxycyclic quaternary ammonium group which is completed with 2 via an appropriate linking group L1 may be included. In this case, we will use the so-called dimer Keyakizo.

Preferred examples of the heterocyclic group represented by Z1 include quinolinium, penzimidazolium, viridinium, acrisonium, phenanthridinium, naphthoviridinium, and inquinolinium. More preferred are quinolinium, naphtopyridinium, and penzimidazolium nuclei, and most preferred is quinolinium.

The aliphatic group for R1 is preferably an unsubstituted alkyl group having 1 to 18 carbon atoms, and an alkyl group having 1 to 18 carbon atoms.
It is a substituted alkyl group. Examples of substituents include those mentioned as substitute substituents for z1.

R1 is preferably an alkynyl group, most preferably a pro-zorugyl group.

Q is an atomic group necessary to form a 4- to 12-membered non-aromatic hydrocarbon ring or non-aromatic heterocycle.

These rings may be further substituted with the groups mentioned for the f substituent of z1.

In the case where X and X are carbon atoms as a non-aromatic hydrocarbon ring, for example, cyclocomplentane, cyclohexane,
Examples include rings such as cyclohexene, cyclohebutane, indane, and tetralin.

Non-aromatic heterocycles include those containing nitrogen, oxygen, sulfur, selenium, etc. as heteroatoms, and for example, when X is a carbon atom, tetrahydrofuran, tetrahydropyran, butyrolactone, pyrrolidone, tetrahydrothiophene, etc. The ring can be mentioned. When X is a nitrogen atom, examples include rings such as pyrrolidine, piperidine, biridone, piperazone, perhydrothiazine, tetrahydroquinoline, and indoline.

The ring nucleus formed by Q is preferably when X is a carbon atom, especially cyclopentane, cyclohexane,
These include cyclohebutane, cyclohexene, indane, tetrahydropyran, and tetrahydrothiophene.

Some of the alkynyl groups to which at least one of the substituents of R1 and z1 and the substituents of Q correspond have already been partially described, but to explain in more detail:
Preferably, it has 2 to 18 carbon atoms, such as nitinyl group, propargyl group, 2-phthynyl group, 1-methylbro-zorugyl group, 1,1-dimethylbro-zorugyl group, 3
-butynyl group, 4-pentynyl group, etc.

Furthermore, these may be substituted with the groups mentioned as the substituents for Z1. As these alkynyl groups, pro-
A zerugyl group is preferred, most preferably when R1 is a pro/4'rugyl group.

As the adsorption promoting group to silver halide that can be formed by the substituents R1, Q and z1, those represented by X1+L1+ are preferable.

Here, X1 is an adsorption promoting group to silver halide, and L1
is a divalent linking group. m is 0 or 1. Preferred examples of the adsorption-promoting group to silver halide represented by X1 include a thioamide group, a mercabuto group, and a 6-membered nitrogen-containing heterocyclic group such as S, L.

These may be substituted with the substituents mentioned for z1. The thioamide group is preferably an acyclic thioamide group (eg, thiou 1/tan group, thioureido group, etc.).

As the merkabuto group of X', in particular, heterocyclic merkabuto F? (e.g. 5-mercapto-tetrazole, 3-mercapto-1.2.4-}lyazole), 2-mercapto1.3.4-thia-soazole, 2-mercap}-1
．． 3,4-oxadiazole, etc.) are preferred.

The 5- to 6-membered nitrogen-containing p ring represented by X1 is composed of a combination of 9 atoms, oxygen, sulfur, and carbon,
Preferred are those that produce iminosilver, such as penzotriazole and aminothiazole.

The divalent linking group represented by L1 is 01N,S
, O. Specifically, for example, an alkylene group, an alkenylene group,
Alkynylene group, arylene group -O- -S- -
NH− −N=, − c o − − so2−(
These groups may have substituents), etc. alone or in combination.

0 0 1111 -OCNH-, -NHCNH-, -NHSO2NH-,
-(Al0 11 Kylene+-CNH-,-(Alyrlene+SO2NH-,
0 O and so on are preferred.

Counter ions/Y for e-load balance include, for example, bromide ion, chloride ion, iodide ion, p-toluenesulfonate ion, ethylsulfonate ion, perchlorate ion, trifluoromethanesulfonate ion, thiocyanate ion, Examples include BF4- ion and PF6- ion.

Among the compounds represented by the general formula [''N-11, those having an adsorption-promoting group to silver halide are preferred, particularly when the adsorption-promoting group X1 is a thioamide group, an azole group, or a heterocyclic mercabuto group. is even more preferable.

Examples of these compounds and their legal methods are disclosed in, for example, the patent application filed in 1983.
No. 2-17,984 and the patents or documents cited in No. 2-17,984.

Specific examples of the compound represented by the general formula CN-1) are listed below, but the present invention is not limited thereto.

(N-1-1) (N-1-5) (N-1-2) CH2C=CH (N-1-6) CH2CmiCH (N-1-3) (N-I-7) S CH2C Mi CH (N-1-4) CH2C Mi CH (N-1-8) CH2C Mi CH CH2C}I Mi CH (N-1-9) (N-1-1 2) (N-!-20) C }12Cmi α CH2cECH (N-1 l 3 ) CH2 (￥H (N-18- !1 l 4 ) ↑ CH2C-CH (N-1 1 5 ) CH2C7虻H (N-1 l 6 ) CH2 re-possible H (N-12!) S CH2CEECH (N-1-23) S CH2αH (N-I-24) SH (:H2σUl-1) Disclosure
) Magazine Black 22.534 (published January 1983, 50-54
Page) and U.S. Patent #'4,471,
It can be synthesized by the method described in No. 044 and similar methods.

General formula (N-If) (wherein, R21 represents an aliphatic group, aromatic group, or heterocyclic group; R22 represents a hydrogen atom, an alkyl group, an aralkyl group, a ryoryl group, an alkoxy group, an aryloxy group) ,X
represents an amino group; G represents a carbon diyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, or an iminomethylene group (HN=C,), and R23 and R24 are both hydrogen atoms, or one of them is a hydrogen atom. and the other one represents any one of an alkylsulfonyl group, an arylsulfonyl group, or an acyl group. However, the hydrazone structure CN-N=(
) may be formed. Furthermore, the groups described above may be substituted with a substituent, if possible. ) In the general formula (NU), the aliphatic group represented by R21 is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

The aromatic group represented by R21 is a monocyclic or bicyclic aryol group, such as a phenyl group or a naphthyl group.

The heterocycle for R21 is a 3- to 10-membered saturated or unsaturated heterocycle containing at least one of N, O, or S atoms, and these may be monocyclic,
Furthermore, a fused metal ring may be formed with other aromatic rings or heterocycles. The heterocycle is preferably a 5- to 6-membered aromatic heterocycle, such as a pyridyl group, a quinolinyl group, an imidazolyl group, a penzimidazolyl group, etc. R21 may be substituted with a substituent. Examples of the substituent include the following. this? The group may be further substituted.

For example, alkyl groups, aralkyl groups, alkoxy groups, alkyl or aryl groups, substituted ano groups, acylamino groups, sulfonylamino groups, ureido groups, urethane groups, aryloxy groups, sulfamoyl groups, carbamoyl groups,
Examples include aryl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halodane atom, cyano group, sulfo group, and carboxyl group.

These groups may be linked to each other to form a ring when possible.

R21 is preferably an aromatic group, an aromatic heterocycle or an aryl-substituted methyl group, and more preferably an aryl group.

Among the groups represented by R2, preferred are: - When G is a carbonyl group, a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxyprobyl group, a 3-methanesulfonamide group); (pil group, etc.),
Aralkyl group (e.g. 0-hydroxybenzyl group etc.)
, Ryoryl group (e.g. hafenylg, 3.5-dichlorophenyl group, 0-methanesulfonadophenyl group, 4-
(methanesulfonylphenyl group, etc.), and hydrogen atoms are particularly preferred.

Furthermore, when G is a sulfonyl group, R2■ is an alkyl group (e.g. methyl group, etc.), an aralkyl group (e.g. 0-hydroxyphenylmethyl group etc.), an aryl group (e.g. phenyl group etc.) or a transmuted amino group ( For example, dimethylamino (dimethylamino) and the like are preferred.

As the substituent for R22, in addition to the substituents listed for R21, for example, an aryl group, an acyloxy group, an alkyl or aryloxycarbonyl group, an alkenyl group, an alkynyl group, or a yanitro group can be used.

These substituents may be further substituted with these substituents. Further, if possible, these groups may be linked to each other to form a ring.

R21 or R22, especially R2, preferably contains a diffusion-resistant group such as a coupler, a so-called ballast group. stomach. The ballast group has 8 or more carbon atoms and is composed of a combination of one or more of an alkyl group, a phenyl group, an ether group, an amide group, a ureido group, a urethane group, a sulfonamide group, and a thioether group.

R21 or R2■ is a compound represented by general formula (N-1). % may have a group X2+L2 force n that promotes adsorption to the surface of silver chloride grains.

Here, X1 represents the same meaning as X1 of the general formula (N-1''l), and is preferably a thioamide group (excluding ``thiosemicarbazide and its S'' substituted group), a mercabuto group, or a 5k
It is a 6-membered nitrogen-containing heterocyclic group.

L2 represents a divalent linking group, general formula 1: N-1)
It expresses the meaning opposite to L1. m2 is O or l.

More preferably, X2 is a cyclic thioamide group (i.e., a mercapto-substituted nitrogen-containing heterocycle, such as a 2-mercaptothiadiazole group, a 3-mercap}-1.2.4-triazole group, a 5-mercaptotetrazole group, a 2- mercapto-1.3.4-oxadiazole group, 2-mercaptobenzoxazole group, etc.), or a nitrogen-containing heterocyclic group (eg, penzotriazole group, penzimidazole group, indazole group, etc.).

Hydrogen atoms are most preferred as R25 and R24.

G in general formula (N-11) is most preferably a carbonyl group.

Further, as the general formula (N-I!), those having an adsorption group to silver halide are more preferable (. A particularly preferable adsorption group to silver halide is the above-mentioned general formula (N-1). These include the mercapto group, cyclic thioamide group, and nitrogen-containing heterocyclic group mentioned above.

Specific examples of the compound represented by general formula (N-I1) are shown below. However, the present invention is not limited to the following compounds.

(N-11-1) (N-11-6) 0 (N-1-7) 0 (N-n-4) (N-1-8) (N-1-5) (N-It-9 ) 0 (N-n 1 0 ) (N-I1- 1 1 ) (N-It-12) SH (N-I[- 1 3 ) (N-I1- 1 8 ) S (N-n-19) (N-If-21) CH2CH2SH (N-I1 1 4) S}{ (N- It 15) ST{ (N-It-16) (N-I1-17) O (N-11-22) H ( N-!I-23) (N-11-24) 3 H The method for synthesizing the compound represented by the general formula (N-) used in the present invention is described, for example, in Research Disclosure Magazine 1. 5,162 (January 1976, pages 76-77), 22,534 (January 1983, pages 50-54), and A23.510 (November 1983, pages 346-3)
(page 52) and U.S. Patent No. 4,08
No. 0,207, No. 4,269,924, No. 4,276, 364, and so on.

In the present invention, general formulas (N-1) and (N-
The compound represented by 11] may be contained in any layer of the photographic material, but it is preferably contained in the silver halide emulsion layer. There is no particular limit to the amount used, but approximately IXIO'' per mole of silver in the silver halide emulsion layer.
A range of from '8 moles to about IXIO-2 moles is useful, preferably from <4 to about IXIO-7 moles per mole of silver.
It is 0 mole.

In order to further enhance the effect of the nucleation promoter of the present invention, it is preferable to use the following compounds in combination.

Hydroquinones (e.g. U.S. Pat. No. 3,227,5
Compounds described in No. 52, No. 4, 2 7 9, 9 8 7)
; chromans (e.g. U.S. Pat. No. 4,268,6
2 1, JP-A-54-103031, and Research Disclosure No. 18264 (1979); Quinones (for example, compounds described in Research Disclosure Zoya No. 21206 (1981)); For example, U.S. Patent No. 4150993 and Japanese Unexamined Patent Publication No. 58
-174757); Oxidizing agents (e.g., compounds described in JP-A-60-260039 and Research Disclosure No. 16936 (1978)); Catechols (e.g., JP-A-55-21013 and Research Disclosure No. 16936 (1978));
Compounds that release nucleating agents during development (e.g., compounds described in JP-A-60-107029); Thioureas (e.g., JP-A-60-107029);
5533); spirobisindanes (for example, the compounds described in JP-A-55-65944);

In addition, in the present invention, it is preferable to use a nucleating agent represented by the general formula (N-D), and the following (1
It is particularly preferable to adopt the modes shown in the order of ) to (8), and the case (8) is most preferable.

(1) When the f substituent has a group promoting adsorption to silver halide represented by X1.

? 2) In specification (1), when the adsorption-promoting group to silver halide represented by

(3) When the simple ring destroyed by 2 at <21 K is quinolinium, inquinolinium, naphthoviridinium, or penzothiazolium.

(4) In the above (2), when the heterocycle completed by 2 is quinolinium.

(5) In PIU (2), R , R or Z
has an alkynyl group as a substituent.

<6) In the above (5), when Rt is a prol-cergyl group.

(7) In the above (2), the thioamide group of x1 is a thiourethane group, and the heterocyclic mercapto group of X1 is a merkabutotetrazole.

(8) In the above (6), when R 1 or 2 is combined with a complete #: heterocycle to form a ring.

In addition, when using a nucleating agent represented by the general formula (N-1f:I), it is particularly preferable to adopt the modes shown in the following order of <11 to (6), and the case shown in (7) is the most preferable. Mashi L.

(1) A case in which a substituent is a group that promotes adsorption to silver halide represented by X2.

{2}! ! In Section 1 (1), when the adsorption promoting group to silver halide represented by

(3) In Jingji (2), when the group represented by G-R22 is a formyl group.

(4) In the above (3), when R23 and R24 are hydrogen atoms.

(5) In the above (3), when R21 is an aromatic group.

(6) In Kawaki (2), when the mercapto group represented by X is 5-mercaptotetrazole or 5-mercapto-1.2.4-1-riazole.

The above general formulas (N-1) and (N-11) can also be used in combination.

Next, the compound of general formula (+) of the present invention will be described.

General formula (!)? The longest wavelength absorption maximum on silver halide expressed is 59
0 nm or less cyanine dye "In the formula, z, and z12 may be rho or different fj, and represent a 5- or 6-membered nitrogen-containing ring nucleation group, and ■11 is 0 or 1. More preferable heterocyclic nuclei include, when l11 is 00, z, and Z1 may be the same or different, and include theazole, pezothiazole, naphthothiazole, zohydronaphthothiazole, and selenazole. , penzoselenazole, naphthoselenazole, dihydronaphthoselenazole, oxazole, penzoxazole, naphthoxazole, penzimidazole, nantoimidazole, pyridine, 'quinoline, imidazo(4.5-b) quinokideline or 3.3
-Heterocyclic nucleus such as zoalkylindolenine, engineering 11
When is 1, 2,, is thiazoline, thiazo? , penzothiazole, selenazoline, selenazole, penzoselenazole, oxazole, penzoxazole, naphthoxazole, imidazole, penzimidazole, naphthoimidazole, birolin, etc.
1■ is oxazoline, oxazole, pedoxazole, naphthoxazole, thiazoline, selenazoline,
This is the case when it represents a heterocyclic nucleus such as pyrroline, pezimidazole or na7timidazole.

The nitrogen-containing heterocyclic rings represented by 21 and z1 may have one or more substituents. Examples of preferable elephant substituents include a formal alkyl group (branched or further substituent {for example, a hydroxy group, a hydrogen atom, an aryl group, an aryloxy group, an arylthio group, a carpoxy group, an alkoxy group, an alkylthio group). group, alkoxycarponyl group, etc.}
It may have. More preferably an alkyl group having a total carbon number of 10 or less. For example, methyl group, ethyl group, butyl group, chloroethyl group, 2,2,3.3-tetrafluoroprobyl group, hydroxy group, benzyl group, tolylethyl group, phenoxyethyl group, phenylthioethyl group, carboxyprobyl group, Examples include methoxyethyl group, ethylthioethyl group, and ethoxycarponylethyl group. )
, a lower alkoxy group (which may further have a substituent).

Examples of the substituent include the same substituents as those listed as examples of the substituents for the alkyl group described elsewhere. More preferably an alkoxy group having a total carbon number of 8 or less, such as a methoxy group, an ethoxy group, a pentyloxy group, an ethoxymethoxy group, a methylthioethoxy group, a phenoxyethoxy group,
Examples include hydroxyethoxy group and chloropropoxy group. ), hydroxy group, halogen atom, cyano group, aryl group (e.g., phenyl group, tolyl group, anisyl group, chlorophenyl group, carboxyphenyl group, etc.), aryloxy group (e.g., tolyloxy group, anisyloxy group, phenoxy chlorophenoxy group), arylthio group (e.g., tolylthio group, chlorophenylthio group, phenylthio group), lower alkylthio group (substituents that may be further substituted? For example, substitution of the above-mentioned lower alkyl group) Examples of the group include those listed above. More preferably, an alkylthio group having a total carbon number of 8 or less, such as a methylthio group, an ethylthio group, a hydroxyethylthio group, a carpoxyethylthio group, a chloroethylthio group, pendyltheo group, etc.), acylamino group (more preferably acylamino group having a total carbon number of 8 or less, such as acetylamino group, benzoylamino group, methanesulfonylamino group, benzenesulfonylamino group, etc.), carpoxy group, lower alkoxy carbonyl group (more preferably an alkoxycarbonyl group having a total carbon number of 6 or less, such as an ethoxycarbonyl group, a ptoxycarbonyl group, etc.), a perfluoroalkyl group (more preferably a total carbon number of 5 or less) Alkyl groups, such as trifluoromethyl groups, difluoromethyl groups, etc.) and acyl groups (more preferably 8 carbon atoms in total)
The following acyl groups, such as acetyl group, propionyl group,
penzoyl group, benzenesulfonyl group, etc.).

Specific examples of the nitrogen-containing ring nucleus represented by Z11 and Z12 include thiazoline, 4-methylthiazoline, thiazole, 4-methylthiazole, 4,5-monomethylthiazole, 4-phenylthiazole, penzothiazole, 5
-Methylbenzothiazole, 6-methylbenzothiazole, 5-ethylpenzothiazole, 5.6-dimethylbenzothiazole, 5-methoxybenzothiazole, 6-
Methoxypenzothiazole, 5-butoxybenzothiazole, 5.6-dimethoxybenzothiazole, 5-methoxy-6-methylbenzothiazole, 5-chloropenzothiazole, 5-chloro-6-mef-rupenzothiazole, 5- Fe-lupenzothiazole, 5-acetylaminobenzothiazole, 6-propioelaminopenzothiazole, 5-hydroxyhenzothiazole, 5-hydroxy-6-methylhenzothiazole, 5-ethoxycal-benzothiazole, 5-carboxybenzothiazole, nat(1.2-d)thiazole, naphtho[2,
1-d) Thiazole, 5-methylnaphthoCl. 2-d]
Thiazole, 8-methoxynaphtho(1,2-d]thiazole, 8,9-dihydronaphthotheasol, 3,3-diethylindo1/nin, 3,3-diglopylindolenine, 3,3--)meth f-ruindolenine, 3.3.5-trimethylindolenine, selenazoline, selenazole,
Penzose I/nazole, 5-methylpenzoselenazole, 6-methylpenzoselenazole, 5-methoxybenzoselenazole, 6-methoxybenzoselenazole, 5-
Chlorobenzoselenazole, 5.6-dimethylbenzoselenazole, 5-hydroxybenzoselenazole, 5-
Hydroxy-6-methylbenzoselenazole, 5,6-
Dimethoxybenzoselenazole, 5-ethoxycarbonylbenzoselenazole, Nantes (1.2-d:l selenazole, naph} [:2.1-d) selenazole, oxazole, 4-methyloxazole, 4,5-dimethyloxazole, 4-phenyloxazole, penzoxazole, 5-hydroxybenzoxagul, 5-methoxybenzoxazole, 5-7enylbenzoxazole, 5-phenethylbenzoxazole, 5-phenoxybenzoxazole , 5-chloropenzoxazole, 5-chloro-6-methylbenzoxagul, 5-7
enylthiobenzoxazole, 6-ethoxy-5-hydroxybenzoxazole, 6-methoxybenzoxazole, naphtho[:1. 2-d:l oxazole,
Nut (2.1-d) Oxazole, Na7} [”
2.3-d] Oxazole, 1-ethyl-5-cyanobenzimidazole, 1-ethyl-5-chloropenzimidazole, 1-ethyl-5.6-dichlorobenzimidazole, 1-ethyl-6-chloro-5-cyano Penzimidazole, 1-ethyl-6-k01:l-5-}! 7
Fluoromethylbenzimitasole, 1-probyl-5
-butoxycarbonylbenzimidazole, 1-pensol-5-metersulfonylpenzimitazole, 1-7
1.1-5-chloro-6-acetylbenzimidazole, 1-ethylnanth(1.2-d,)imidazole,
1-ethyl-6-chloronaphtho(2.3-d) imidazole, 2-quinoline, 4-quinoline, 8-fluoro-4
-quinoline, 6-methyl-2-quinoline, 6-hydroxy-2-quinoline, 6-methoxy-2-quinoline and the like.

R,, and R1. represents an optionally substituted alkyl group or alkenyl group, which may be a single bar or different, and have a total of 10 or less carbon atoms. More preferable lattice substituents for alkyl and alkenyl groups include, for example, a sulfo group, a carboxy group, a halodane atom, a hydroxy group, an alkoxy group having 6 or less carbon atoms, an optionally substituted aryl group having 8 or less carbon atoms ( (e.g., phenyl group, tolyl group, sulfophenyl group, carpoxyphenylene group, etc.), heterocyclic group (e.g., furyl group, theenyl group, etc.), optionally substituted aryloxy group having 8 or less carbon atoms (e.g., Oa phenoxy group, phenoxy group, sulfo-7 enoxy group, hydroxyphenoxy group), noacyl group with 8 carbon atoms (?lJ,
t[, benzenesulfonyl group, methanesulfonyl group, acetyl group, probionyl group, etc.), alkoxycarbonyl group with 6 or less carbon atoms (e.g., ethoxycarbonyl group, butoxycarbonyl group, etc.), cyano group, 6 or less carbon atoms alkylthio groups (e.g., methylthio group, ethylthio group, etc.), optionally substituted arylthio groups with 8 or less carbon atoms (e.g., phenylthio group, tolylthio group, etc.), optionally substituted carbamoyl groups with 8 or less carbon atoms groups (e.g., carbamoyl group, N-ethylcarbamoyl group, etc.),
Examples include acylamino groups having 8 or less carbon atoms (eg, acetylamino group, methanesulfonylamino group, etc.).

One or more substituents may be present.

Specific examples of the groups represented by R1 and R1■ include, for example, a methyl group, an ethyl group, a probyl group, an allyl group, a pentyl group, a hexyl group, a methoxyethyl group, an ethoxyethyl group,
Phenethyl group, tolylethyl group, sulfophenethyl group,
2,2.2-trifluoroethyl group, 2.2,3.3-
Tetrafluoroprobyl group, carbamoylethyl group, hydroxyethyl i, 2-(2-hydroxyethoxy)ethyl group, carboxymethyl group, carpoxyethyl group, ethoxycarbonylmethyl group, sulfoethyl group, 2-? Rolow 3-sulfofuropyl group, 3-sulfoprobyl group, 2
-Hydroxy-3-sulfoprobyl group, 3-sulfoptyl group, 4-sulfophthyl, l, 2-(2,3-dihydroxypropyloxy)ethyl group or 2-(2-(3-
Examples include sulfoprobyloxy)ethoxy]ethyl group.

R13 and R15 represent hydrogen atoms. Also, Ri3 is R
11 and R15 may be linked to R1■ to form a 5- or 6-membered ring.

R14 is a hydrogen atom or a lower alkyl group (which may be substituted, such as a methyl group, an ethyl group, a proyl group,
Methoxyethyl group, phenethyl group, etc.

More preferably O represents << is an alkyl group having 5 or less carbon atoms) X,1 represents an acid anion residue.

"11 represents O or 1, and is 0 in the case of an inner salt."

Among the sensitizing dyes represented by the general formula (1), a more preferable sensitizing dye is one in which ■11 represents 1 and Z11 represents O? Represents a heterocyclic nucleoform atomic group such as sasol, penzoxazole, naphthoxazole, etc., and Z1 represents a heterocyclic nucleoform antigen group such as penzimidazole or naphthoimidazole [2,
, and zt2 may have one or more substituents as described above, but when Z1 represents a penzimidazole nucleus or a naphthoimidazole nucleus, the radical attracting substituent is preferable. ], R1, and R1■ represent a group having a sulfo group, a carpoxy group, or a hydroxy group, and R14 represents a hydrogen atom.

Among the sensitizing dyes represented by general formula (I), in particularly preferred cases, Z1 represents an atomic group forming a penzoxazole nucleus, z, 2 represents an atomic group forming a penzimidazole nucleus, and at least one of R11 and R12 represents a group containing a sulfo group or a carboxy group, R14 represents a hydrogen atom, and IN represents 1. The heterocyclic nucleus represented by z11 and Z1■ may have one or more substituents as described above, but which substituents are particularly preferable? In the case of a penzimidazole nucleus, a chlorine atom, a futsun atom, a cyano group, an alkoxycarponyl group with a total carbon number of 5 or less, an acyl group with a total carbon number of 7 or less, or a trifluoromethyl group with a carbon number of 4 or less When the perfluoroalkyl group is another heterocyclic nucleus, an optionally substituted phenyl group with 8 or less carbon atoms, an alkyl group with 5 or less carbon atoms, an alkoxy group with 5 or less carbon atoms, or a total carbon number of 5 or less Examples include an acylano group, a carboxy group, an alkoxycarbonyl group having a total carbon number of 5 or less, a pen-sol group, a phenethyl group, or a chlorine atom.

Specific examples of the compound represented by general formula (1) are shown below.

1-1 ■ 2 ■ 3 So, K SO, I 4 I - 9 ■ l O! l l (CH2ノ,SO3 C2H5 ■ 5 1-7 ■ 8 ■ 1 3 ! 1 5 I -22 I 23 ! -24 The compound represented by the general formula (1) is a known compound, for example, 104,917, 1977, special public service 1977-
25,652, the specification of Japanese Patent Publication No. 57-22,368, etc., and F. M. Hamer + The Chemises
Try of Heterocyclic Compou
nds. Vol. 18+TheCyanine Dy
e@and Related Compounds,
A. W*issberger ed. ．． Inter
science, New York, 1964.
,D. M. Sturmer, The Chemi
Try ofHeterocyclic Compo
unds, Vol. 3 0 + A. Weissbe
rger and E. C. Taylor ed. r
John Willy, New York, p. 4
4 1. You can synthesize it by referring to etc.

The nucleation accelerator useful in the present invention is represented by the following general formula (■).

General formula (II) -28 (CH2ノ3S03Na (CH2),S03 A-E-G Y + VR) m In the formula, A represents a group adsorbed to silver halide.

Examples of the group adsorbed on silver halide include compounds having a mercapto group bonded to a heterocycle, heterocyclic compounds capable of producing iminosilver, or hydrocarbon compounds having a mercapto group.

Examples of mercapto compounds bonded to the cylindrical ring include p-Zen or unsubstituted mercaptoazole M (e.g. 5-
Mercaptotetrazoles, 3-mercapto-1.2.
4-}Riazoles, 2-mercabutoimidazoles,
2-mercapto L3, 4-thiazoazoles, 5-mercabuto-1,2,4-thiadiazoles, 2-mercapto-1,3°,4-oxadiazoles, 2-mercabuto-1.3.4-selena Diazoles, 2-mercaptooxazoles, 2-mercaptothiazoles, 2-
mercaptopenzoxazoles, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, etc.), substituted or unsubstituted mercaptopyrimidines (
Examples include 2-merkabutovirimidines, etc.).

Examples of heterocyclic compounds capable of forming iminosilver include substituted or unsubstituted indazoles, penzimidazoles, penzotriazoles, penzoxazoles, penzuthiazoles, imidazoles, thiazoles, oxazoles, triazoles, Examples include tetrazoles, azaindenes, pyrazoles, and indoles.

Examples of hydrocarbon compounds having a mercapto group include alkylmercaptans, arylmercaptans, alkenylmercaptans, and aralkylmercaptans.

Y represents a divalent linking group consisting of an atom or a group of atoms selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. As a linking group for two letters, for example, -S- 10- -N- ? These connecting groups are a direct nephew or a branched alkylene group (e.g. methylene group, ethylene group, propylene group, butylene group, hexylene group, 1-
methylethylene group, etc.), or a substituted or unsubstituted arylene group (phenylene group, naphthylene group, etc.).

R1, R2, R3, R4, R5, R6, R7, R8, R
, and R,. is a hydrogen atom, a substituted or unsubstituted alkyl group (e.g., methyl group, ethyl group, proyl group, n-butyl group, etc.), a substituted or unsubstituted aryl group (e.g., phenyl group, 2-methyl 7-enyl group, etc.) basis,
etc.), a substituted or unsubstituted alkenyl group (eg, propenyl group, 1-methylvinyl group, etc.), or a substituted or unsubstituted aralkyl group (eg, penzyl group, phenethyl group, etc.).

R represents an organic group containing at least one thioether group, amino group (including salt form), ammonium group, ether group, or heterocyclic group (including salt form). Such 5-aryanagi groups include substituted or unsubstituted alkyl groups,
Examples include combinations of groups selected from alkenyl groups, aralkyl groups, or aryl groups and the above groups, but combinations of these groups may also be used. For example, dimethylaminoethyl group, aminoethyl group, dietheraminoethyl group, dibutylaminoethyl group, dimethylaminoethyl group, dimethylaminoethylthioethyl group, dimethylaminoethylthioethyl group, 4-
Dimethylaminophenyl group, 4-dimethylaminobenzyl group, methylthioethyl group, ethylthioprobyl group, 4
-Methylthio-3-cyanophenyl group, methylthiomethel group, trimethylammonioethyl group, methoxyethyl group, methoxyethoxyethoxyethyl group, methoxyethylthioethyl group, 3.4-/methoxyphenyl group, 3
-chloro-4-methoxy7enyl group, morpholinoethyl group, l-imidagrilyethyl group, morpholinoethylthioethyl group, pyrrolidinoethyl group, piperidinoglovir group, 2-pyridylmethyl group, 2-(1-imidazolyl group) ) Ethylthioethyl group, pyrazolylethyl group, triazolylethyl group, methoxyethoxyethoxyethoxycarboylaminoethyl group, etc. n represents O or 1; m represents l or 2;

Among the compounds represented by the general formula (It), preferred compounds are represented by the following general formulas (III) to (■).

General formula (I [I) In general formula (III), Q preferably forms a 5- or 6-membered heterocycle composed of at least one of carbon atom, nitrogen atom, oxygen atom, sulfur atom, and selenium atom. represents the atomic group necessary to

The heterocycle may also be fused with a carbon aromatic ring or a heteroaromatic ring.

Examples of the heterocycle include tetrazoles, triazoles, imidazoles, thiadiazoles, oxasoazoles, selenadiazoles, ox"j-1-k'JR,
Examples include thiazoles, penzoxazoles, penzothiazoles, penzimidazoles, and pyrimidines.

M is a hydrogen atom, an alkali metal atom (e.g. sodium atom, potassium atom, etc.), an ammonium group (e.g. trimethylammonium group, dimethylpendylammonium group, etc.), under alkaline conditions M=H or an alkali metal atom; It represents a diluent group (eg, acetyl group, cyanoethyl group, methanesulfonylethyl group, etc.).

In addition, these heterocycles include a nitro group, a halogen atom (e.g., chlorine atom, bromine atom, etc.), a mercapto group, a cyano group, a substituted or unsubstituted alkyl group (e.g.,
methyl group, ethyl group, probyl group, t-butyl group, cyanoethyl group, etc.), aryl group (e.g. phenyl group, 4
-methanesulfonamidophenyl group, 4-methylphenyl group, 3,4-dichlorophenyl group, naphthyl group, etc.)
, alkenyl groups (e.g. allyl group, etc.), aralkyl groups (e.g. penzyl group, 4-methylbenzyl group, phenethyl group, etc.), sulfonyl groups (e.g. methanesulfonyl group, ethanesulfonyl group, p-}luenesulfonyl group, etc.) ), carbamoyl group (e.g. unsubstituted carpamoyl group, methylcarbamoyl group, phenylcarbamoyl group, etc.),
Sulfamoyl group (e.g., unsubstituted sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, etc.), carpanamide group (e.g., acetamide group, penzamide group, etc.), sulfonamide group (e.g., methanesulfonamide group, benzene group, etc.) sulfonamide group, p-toluenesulfonamide group, etc.), acyloxy group (e.g. aceteloxy group, penzoyloxy group, etc.), sulfonyloxy group (e.g. methanesulfonyloxy group, etc.)
, ureido group (for example, unsubstituted ureido group, methylureido group, ethylureido group, phenylureido group, etc.)
, thioureido group (e.g., unsubstituted thioureido group, methylthioureido group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.), oxycarbonyl group (e.g., ehamethoxycarbonyl group, phenoxycarbonyl group, etc.)
, oxycarponylamino group (e.g. methoxycarponylamino group, phenoxycarponylamino group, 2-ethylhexyloxylcarbonylamino group, etc.), carboxylic acid or its salt, sulfonic acid or its salt, hydroxyl group, etc. However, from the viewpoint of the nucleation promoting effect, it is preferable not to be substituted with a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, or a hydroxyl group.

Preferred examples of the heterocycle represented by Q include tetrazoles, triazoles, imiguzole, thiadiazole, and oxadiazole.

Y, R, m, and n each have the same meaning as in general formula (It).

General formula (IV) where Y-s R - mSn. ．． M is the general formula ((l)
, and Q' is 5 which can be formed with iminosilver.
Or it represents a group of atoms necessary to form a 6-membered hydrogen ring. It represents an atomic group necessary to form a 5- or 6-membered heterocycle preferably selected from carbon, nitrogen, oxygen, sulfur, and selenium. Further, this heterocycle may be fused as a carbon aromatic ring or a heteroaromatic ring. Examples of the heterocycle formed by Q' include indazoles, penzimidazoles, penzotriazoles, penzoxazoles, penzuthiazoles, imiguzoles, thiazoles, oxazoles, triazoles, tetrazoles, and tetraadeindene. Examples include triazaindenes, diadeindenes, pyrazoles, indoles, and the like.

In the formula, Ms R% Y% n is the same as that in the general formula (IE!). X represents an oxygen atom, a sulfur atom or a selenium atom, with a sulfur atom being preferred.

General formula (M) R'' In the formula, R' is a hydrogen atom, a halokene atom (for example, a chlorine atom, a bromine atom, etc.), a nitro group, a mercapto group, an unsubstituted amino group, or a substituted or unsubstituted alkyl group, respectively. groups (e.g., methyl group, ethyl group, etc.), alkenyl groups (e.g., propenyl group, 1-methylvinyl group, etc.), aralkyl groups (e.g., penzyl group, phenethyl group, etc.)
, an aryl group (eg, phenyl group, 2-methylphenyl group, etc.), or +Y +VR.

R” is a hydrogen atom, an unsubstituted amino group, or {YiR
, and when R' and R'' represent +Y}iR, they are mutually L
・Can be the same or different.

However, at least one of R' and R" is +y −}T
-p. represents.

M,RSY. ．． nit has the same meaning as each of the above general formulas ([[).

General formula (■) In the formula, R″′ represents +Y6R. However, M, R, Ys
n has the same meaning as each of the above general formula (Ill).

General formula (■) represents a diyl group, 1-methylvinyl group, etc.), an aralkyl group (eg, benzyl group, phenethyl group, etc.), or an aryl group (eg, phenyl group, 2-methylphenyl group, etc.).

M and R"' are the same as each of the above general formula (■), respectively.

Specific compounds represented by formulas (II) to (VI) of the present invention are shown below, but the compounds of the present invention are not limited thereto.

n-1 In the formula, R and R are hydrogen atoms, halogen atoms (e.g., chlorine atoms, bromine atoms, etc.), substituted or unsubstituted amino groups (e.g., unsubstituted amino groups, methylamino groups, etc.), nitro groups, respectively substituted or unsubstituted alkyl groups (e.g. methyl group, ethyl group, etc.), alkenyl groups (
For example, Grope 1I-2 ■-93 ■ 4 SH ■ 5 ■ 1 1 ■ 1 2 ■ 1 3 D 1 4 ■ - 7 ■-8 ■ 9 ■ 110 ■ - 1 5 ■ 1 6 ■- 17 ■ 1 9 CH3 ■ -20 ■ 2 1 ■ 127 ■ 129 ■ 130 e 23 ■ - 24 ■ 2 5 ■ 26 ■ 3 1 ■ 132 ■ 3 3 ■ - 34 ■ - 3 5 F -39 ■ - 36 O If-40 O ■- 37 H II-' 4 1 H ■- 38 H-42 The nucleation accelerator used in the present invention is
Berichte der Deutschen
Chemtschen Gesellschaft)
28〈77 (1895), Japanese Patent Application Publication No. 1973
-37436, Mukai No. 51-3231, U.S. Patent No. 3,2
No. 95,976, U.S. Patent No. 3,376,310, Berhchte der Deutschen
Chemischen Gesellschaft) 2
2, 568 (1889), 29, 2483 (18
96), Journal of Chemical Society (
J. Chem. Soc. ) 1 9 3 2,
1806, Journal of the American Chemical Society (J. Am. Chem. So
c. ) 7 1, 40 00 (1949), U.S. Pat.
Issue, Advances in Heterocyclic Chemistry
yclic ChemLstry) 9, l65 (1
968), Organic Synthesis
ic$ynthesis) IV, 569 (1963)
, Journal of the American Chemical Society (J.Am.Chem.Soc.) 4 5
, 2390 (1923), Hemisie Perichte (Ch
emischeBert chata) 9, 465 (1
876), JP 40-28496, JP 50-8
No. 9034, U.S. Patent No. 3,106,467,
3, 4 2 0, 6 7 0, 2, 2 7 1,
2 2 9, 3, 1 3 7, 5 7 8, 3
No. 148066, No. 3,5 1 1,6 6 3, No. 3.060,028, No. 3,2 7 1,1 5 4
No. 3,251,691, No. 3,5 9 8,5
9 No. 9, No. 3, 1 4 8, 0 6 6, Special Public Interest Publication No. 4
No. 3-4135, U.S. Patent 3. 6 1 5,616, 3.4 g O, 6 6 4, 3.0 7 1
, 4 No. 65, l'f! 2,4 4 4,6 0 5, 2,4 4 4,6 0 6, 2,4 4 4
, No. 607, No. 2,935,404, Patent Application No. 1983
It can be synthesized by the method described in, for example, No.-145932.

The nucleation accelerator can be contained in the light-sensitive material or in the processing solution, but it can also be contained in the internal latent image type silver halide emulsion layer and other hydrophilic colloids Nj (intermediate layer, protective layer, etc.) in the light-sensitive material. ) is preferable. Particularly preferable (・
layer in or adjacent to the silver halide emulsion.

The amount of nucleation accelerator added is 10- per mole of halodanization.
Preferably 6 to 10-2 mol, more preferably 10
~10 mol.

In addition, when adding the nucleation accelerator to the processing solution, that is, the developer or its pre-bath, 10-8 to 10
-' mol is preferable, more preferably l O-' to 1
It is 0-4 mol.

A non-fogged internal latent image type silver halide emulsion is a silver halide emulsion in which the surfaces of the silver halide grains are not pre-fogged and the latent image is mainly formed inside the grains. More specifically, a certain amount of silver halide emulsion is coated on a transparent support,
When this was exposed to light for a fixed time of 0.01 to 10 seconds and developed for 6 minutes at 20°C in the following developer A (internal type developer), the maximum density measured by the usual photographic density measurement method was , a density that is at least five times greater than the maximum density obtained when a silver halide emulsion coated and exposed in the same manner as above is developed in developer B below (surface type developer) for 5 minutes at 18°C. Surface developer Metol t-ascorbic acid NaBO2' 4H20 KBr Internal developer A with water Metol 2g Sulfite unda' (anhydrous) 90g Hydroquinone 8g Soda carbonate (monohydrate)
52.5, pKB r
59KI Q, 5g
Specific examples of 1t latent type emulsions include British Patent No. 1011062, U.S. Patent No. 2,592,250, and U.S. Pat.
, 4 5 6, 9 4 3 2.5g 11 359 1.9 1t Compaction type silver halide emulsions and core/
Examples include shell-type silver halide emulsions, in which the core/
As a shell type silver halide emulsion, JP-A-47-32
No. 813, flirj No. 47-32814, Ro 52-1
No. 34721, Sono 52-156614, Gej53-6
No. 0222, No. 53-66218, q53-6672
'l, rf! No. 55-127549, No. 57-1366
No. 41, Iif! No. 58-70221, No. 59-208
No. 540, No. 59-216136, No. 60-1076
No. 41, No. 60-247237, No. 61-2148, No. 61-3137, Special Publication No. 56-18939, No. 58-1412, No. 58-1415, No. 58-69
No. 35, No. 58-108528, % Gansho 61-364
No. 24, U.S. Patent No. 3,206,313, Sono No. 3,317,322
No. 3761266, No. 3761276, No. 38
No. 50637, No. 3923513, No. 4035185
No. 4395478, No. 4504570, European Patent No. 0017148, Research Disc R.
Examples include emulsions described in No. D 16345 (November 1977).

In addition to silver chloride and silver bromide, typical silver halide compositions include mixed silver halides such as silver chlorobromide, silver chloroiobromide, and silver iodobromide. The silver halide preferably used in the present invention is silver halide (iodine) bromide, silver (iodine) chloride, or silver (iodine) bromide that does not contain silver iodide or contains less than 3 moles of silver iodide. , the average grain size of silver halide grains (in the case of spherical or near-spherical grains, the grain diameter is taken as the grain size, and in the case of cubic grains, the ridge length is taken as the grain size and the projected area is expressed as the average): It is preferably 0.1μ or more under 2μ, but particularly preferably 1μ or less and 0.15μ or more. The particle size distribution may be narrow or wide, but in order to improve granularity and sharpness, the particle number or weight should be within ±40% (more preferably within ±30%, most preferably within ±30%) of the average particle size. It is preferable to use a so-called "monodisperse" silver halide emulsion in the present invention, which has a narrow grain size distribution in which more than 90, particularly more than 95%, of all grains fall within ±20 degrees. In addition, in order to satisfy the target gradation of the light-sensitive material, two or more types of monodispersed silver halide emulsions with different grain sizes or two or more types of monodisperse silver halide emulsions with the same grain size are used in the emulsion layer having substantially the color sensitivity of B1-. A plurality of particles having different sensitivities can be mixed in the same layer or coated in separate layers. Furthermore, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used by mixing or layering them.

The silver halide particles used in the present invention have regular shapes such as cubes, octahedrons, dodecahedrons, and dodecahedrons.
r), or may have an irregular crystal shape such as a spherical shape, or may have a composite shape of these crystal shapes. Further, tabular grains may be used, and in particular, an emulsion may be used in which tabular grains having a length/thickness ratio of 5 or more, particularly 8 or more occupy 50% or more of the total projected area of the grains. An emulsion consisting of a mixture of these various crystal forms may also be used.

The silver halide emulsion used in the present invention can be prepared in the presence of a silver halide solvent.

As a silver halide solvent, US patent g3.271,1
No. 57, No. 3, 5 3 1, 2 8 9, No. 3.
No. 574628, JP-A No. 54-1019, Ro 15 4
- Organic thioethers described in No. 158917, etc., JP-A-53-82408, Ro 155-77737
It is a thiourea conductor described in No. 55-2982.

The silver halide emulsion used in the present invention can be chemically sensitized inside or on the grain surface by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination.

In addition to the sensitizing dyes of the present invention, the light-sensitive materials used in the present invention include sensitizing dyes such as cyanine dyes and merocyanine dyes described in JP-A No. 55-52050, pages 45 to 53. etc.) can be added.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are listed in Research Disclosure 1.
Volume 76 17643 (published December 1978) Page 23 ■
It is described in sections A-J.

Here, the sensitizing dye etc. can be added at any stage of the photographic emulsion manufacturing process, or can be added at any stage after manufacturing up to just before coating. Examples of the former include particle formation, physical ripening, and chemical ripening.

The emulsion layer or other hydrophilic colloid layer of the present invention may contain a water-soluble dye as a filter dye or for various purposes such as preventing irradiation. As the filter dye, a dye for further lowering the photographic sensitivity or a dye having substantial light absorption mainly in the region of 350 nm to 6'OOnm is used for increasing the safety against safelight light.

These dyes may be added to the emulsion layer depending on the purpose, or they may be added together with a mordant to a non-photosensitive aqueous colloid layer on top of the silver halide emulsion layer, that is, farther from the silver halide emulsion layer with respect to the support. It is preferable to use it by fixing it.

Although it varies depending on the molar absorption coefficient of the dye, it is usually 10-2 g/
It is added in the range of m2 to 1 fi/m2. Preferably it is 50 m9 to 500:n9/m2.

Specific examples of dyes are described in detail in Japanese Patent Application No. 61-209169.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. That is, azoles such as penzothiazolium salts, nitroindazoles, chloropenzimidazoles, promobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, penzothiazoles, nitrobenzos. triazoles, etc.; mercaptopyrimidines: mercaptotriazines; thioketo compounds, e.g. oxazolinthione; azaindenes, e.g. triazaindenes, tetraazaindenes, especially 4-hydroxy substituted (1,3.3a.7) Tetrazaindenes), interazaindenes, etc.; many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamide, etc. can.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomol 7-olins, quaternary ammonium salt compounds, urethane derivatives,
It may also contain developing agents such as urea derivatives, imiguzole derivatives, dihydroxybenzenes, and 3-virazolidones.

Dihydroxybenzenes (hydroquinone, 2
-methylhydroquinone, catecholna) and 3-virazolidones (1-phenyl-3-virazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-virazolidone, etc.) are preferred, and are usually used at a length of 597 m or less. It will be done. In the case of dihydroxybenzenes, 0.0
More preferably 1 to 1 g/m2, and in the case of 3-virazolidones, 0.01 to 0. 2 g/m or more preferred.

The photographic emulsions and non-photosensitive hydrophilic colloids of the present invention may contain inorganic or organic hardeners.

For example, activated vinyl compounds (1.3.5-
to! j acryloyl hexahydro a-triazine,
bis(vinylsulfonyl) methyl ether, N,N'-methylenebis[β-(hinylsulfonyl)glopionamide], etc.), active halodane compounds (2,4-dichloro-6-hydroxy-8-triazinefL.!l”
), mucohaloquine Ma (sodium mucochlorate), N-carbamoylpyridinium [3((1-morpholy)carbonyl-3-pyridinio)methanesulfonate, etc.),
Haloamidinium salts (1-(1-chloroo-1-pyridinomethylene) pyrrolidinium, 2-naphthalenesulfonate, etc.) can be used alone or in combination. Benikamo, Japanese Patent Publication No. 53-41220, No. 53-572
57, bolt 59-162546, (b) 60-80846
and the active vinyl compounds described in U.S. Pat. No. 3,325,
The active halogenides described in No. 287 are preferred.

The photographic emulsion layer or other new aqueous colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
It may contain various surfactants for various purposes such as development acceleration, contrast enhancement, sensitization, etc. For example, saponin (steroid type),
Alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol 1a compound, E') ethylene glycol alkyl ethers or polyethylene glycol alkylaryl ether R. #') Ethylene glycol esters, polyethylene glycol sorbitan S? polyalkylene glycol alkylamines or amides, silicone polyethylene oxide adducts), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides,
Nonionic surfactants such as alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugar; alkylcarpanates, alkylsulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates Acid acid, alkyl sulfate, alkyl phosphate L N-acyl N-7
Carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, such as alkyltaurines, sulfosuccinates, sulfoalkylpolyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc. Anionic surfactants containing acidic groups such as amino acids, aminoalkylsulfonic acids, aminoalkyl TAe or phosphoric acid esters, alkyl betaines, amphoteric surfactants such as amine oxides; alkylamine salts, aliphatic or Cationic surfactants such as aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium, imigzolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

Further, in order to prevent static electricity, it is preferable to use a fluorine-containing surfactant described in JP-A No. 60-80849.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide, barium strontium sulfate, or polymethyl methacrylate in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of preventing adhesion.

The photosensitive material used in the present invention may contain a dispersion of a water-insoluble or releasable synthetic polymer for the purpose of improving film properties. For example, alkyl (meth)acrylates, alkoxy acrylic (meth)acrylates, glycidyl (meth)acrylates,
Polymers containing acrylate alone or in combination, or a combination of these with acrylic acid, methacrylic acid, or 1g of these as monomer components can be used.

? Gelatin is advantageously used as a binder or protective colloid for the emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethyl cellulose,
Cellulose derivatives such as carboxymethylcellulose and cellulose sulfate esters, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly+7+N-vinylpyrrolidos, polyacrylic acid, polymethacrylic acid, and polyacrylic A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polyamide, polyvinylimidazole, polyvinylpyrazole, and the like.

As the gelatin, in addition to coal-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolysates and gelatin enzymatically decomposed products can also be used.

The silver halide emulsion layer used in the present invention may contain polymer latex such as alkyl acrylate. It can be made to contain.

Supports for the photosensitive material of the present invention include cellulose triacetate, cellulose diacetate, nitrocellulose,
Polysterene, polyethylene terephthalate, etc. are used. In particular, it is important for the COM film to have excellent anti-static properties, and a support with good conductivity is preferred.

Various known developing agents can be used to develop the photosensitive material of the present invention. i.e. polyhydroxybenzenes such as hydroquinone, 2-chlorohydroquinone, 2-methylhydroquinone, catechol, pyrogallol; aminophenols such as p
-anophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.; 3-virazolidones, such as 1-phenyl-3-virazolidones, 1-
7enyl-4. 4-zomethyl-3-virazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-
3-virazolidone, 5,5-dimethyl-1-7enyl-3-pyrazolidone, etc.; ascorbic acids, etc. can be used alone or in combination. Specifically, the patent application
Developers such as those described in Meiji No. 6-154116 can be used.

Also, to obtain a dye image in the presence of a dye-type bed coupler, an aromatic primary amine developing agent, preferably a p-phenylenediamine type developing agent, can be used. A specific example is 4-amino-3-methyl-N. N-dimethylaniline hydrochloride, N,N-diethyl-p-phenylenediamine, 3-methyl-4-amino-N-ethyl-N-β-(methane-sulfonamide)ethylaniline, 3
-Methyl-4-amino-N-ethyl-N-(β-sulfoethyl)aniline, 3-ethoxy-4-amino)-N-(β-sulfoethyl)aniline, 4-amino-N-ethyl-N-(β -hydroxyethyl)aniline. This kind of developer is an alkaline-treated Kaimono (
(processing element) or in an appropriate layer of the photosensitive element.

When using the DRR compound in the present invention, any silver halide developer can be used as long as it can cross-meltify the DRR compound.

The developer solution may contain preservatives such as sodium sulfite, potassium sulfite, ascorbic acid, and reductones (for example, piperidinohexose reductone).

A positive image can be directly obtained from the photosensitive material of the present invention by developing it using a surface developer.

The surface developer is one in which the development process is substantially induced by latent images or fog nuclei on the surface of the silver rodanide grains. Although it is preferable to include a silver halide dissolving agent in the developing solution, as long as the internal latent image substantially contributes to the completion of development by the surface development center of the silver halide grains, the silver halide dissolving agent agents (eg sulfites).

The developer contains sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
May include trisodium phosphate, sodium metaborate, and the like. The content of these chemicals is such that the pH of the developer is 10.
~12, preferably l1.5 or less, more preferably IO
．． Select from 0 to 11.0.

The developer may contain a color development accelerator such as benzyl alcohol. The developer also contains fogging agents, such as benzyl-adazoles, such as 5-nitrobenzimidazole; benzotriazoles, such as penzotriazole, 5-methyl-benzotriazole, etc., to lower the minimum density of the direct blur image. It is advantageous to include compounds used as inhibitors.

The present invention will be further explained below with reference to Examples.

Example 1 Emulsion A was prepared by the following method. 1.Δ An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to an aqueous solution of gelatin in a 1,8-dihydroxy-3,6-dithiaoctane solvent over a period of 5 minutes at 75°C with vigorous stirring to obtain an average particle size. The diameter is O. A 15 μm octahedral silver bromide emulsion was obtained. The ρAg of the solution is 83 20! After 11 sections, sodium thiosulfate and chloroauric acid (tetrahydrate) were added to this emulsion in an amount of 115 μm per mole of silver, and the emulsion was heated at 75°C for 50 μm.
Chemical sensitization treatment was performed by heating for minutes. Using the silver bromide grains thus obtained as cores, they were further treated for 40 minutes in the same precipitation environment as in the first precipitation, but while controlling the PAg of the solution to be 7.50, and finally the average grain size was A cubic monodisperse core/shell silver bromide emulsion with a shape of 0.55 μm was obtained. After washing with water and desalting, sodium thiosulfate and chloroauric acid (tetrahydrate) were added to the emulsion in an amount of 3.41 g each per mole of silver, and the emulsion was heated at 75°C for 60 minutes to perform chemical sensitization treatment to form an internal latent image. A type silver halide emulsion A was obtained.

Emulsion A was divided and sensitizing dyes, nucleating agents, and accelerators were added as shown in Table 1, and 4-hydroxy-6-methyl- was added as a stabilizer.
1.3.3.3a-Tetrazaindene and 5-methylbenzotriazole, 1,3-divinylsulfonyl-2-brobanol as hardener were added. On the other hand, as a matting agent in the gelatin solution for the surface protective layer, an average particle size of 1.
Barium strontium sulfate of Oμm, hydroquinone 50eg/rd, compound 2 of the following structure 2 0 @g/
nf, adding sodium p-dodecylbenzenesulfonic acid and a surfactant of the following structural formula (■) as a coating aid,
Ag13g/n? was coated on a polyethylene terephthalate film together with an emulsion layer by a simultaneous coating method. Samples 1 to 3 were prepared by coating the sample to give the following properties.

However, an antihalation layer is previously coated on the opposite side of the support to which the emulsion layer is coated.

■ CaF + SOtNCHtCOOκC 3H
, [Exposure and processing] Using the Fuji Medical Imaging Camera FIM3543AG manufactured by Fuji Medical Systems ■, the image output was output as a negative image (when the standard specification was taken as a positive image), and the sample was cut into half size. 6 frames were exposed. Afterwards, the following treatments were performed, followed by observation and evaluation. Automatic processor: Fuji FPM9 000 (manufactured by Fuji Photo Film ■) Developer: RO-3 ( ) Fixer: Fuji F ( ) Processed with Dry to dry 9 Q'. (Comparative example) Sample 4 Water 1j! Add 30 g of gelatin, 5 g of potassium bromide, and 0.05 g of potassium iodide, and add an aqueous solution of silver nitrate (5 g as silver nitrate) and 0.0 g of potassium iodide to a container kept at 75°C while stirring.
．． An aqueous solution of potassium bromide containing 75 g was added over 1 minute using the double jet method. Further, the addition rate at this time was accelerated so that the flow rate at the end of addition was eight times that at the start of addition. After this, 0.37 g of potassium iodide was added. (
Average particle size: o. es μm, average particle diameter/thickness ratio: 6.5) After the water washing step, 50 g of Gel was added to 150 g of A g N O s and the pH was adjusted to 6.4 to obtain an unripened emulsion. After dissolving this unripened emulsion at 54°C, dye (II) was added first, followed by dye (1), and the mixture was thoroughly stirred. Thereafter, an emulsion was prepared which was chemically sensitized with a sulfur compound and potassium hydrauric chloride as described in US Pat. No. 1,574,944. (C}It) ssQs e(CJ) 3SQ3NaS
03 e SO3H-N(CzHs
) s The emulsion thus obtained was treated with (
A coating solution for an emulsion layer was prepared by adding 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene) and a coating aid.

Furthermore, as a protective layer, a coating aid of bis-type polyethylene oxide, a fluorocarbon surfactant, and an anionic surfactant, a matting agent of polymethyl methacrylate (with an average particle size of 2.0 μm), and a slipping agent of polysiloxane are used. A gelatin solution containing a hardening agent (N,N'-methylene bis[beta-(vinylsulfonyl) propionate)] was prepared.

An emulsion layer and a protective layer are simultaneously coated on a PET support on which an antihalation layer has been previously coated on the opposite side.
It was applied to one side so that the root weight was 3.0g/rrr. [Exposure and processing] A positive image was output using a Fuji Medical Imaging Camera FIM3543AG manufactured by Fuji Medical Systems ■, and a half-cut size sample was exposed for 6 frames.

Afterwards, the following treatments were performed, followed by observation and evaluation. Automatic development va: Fuji FPM9 0 0 0 (
Processed with Fuji Photo Film ■) Developer: RD-3 ( ) Fixer: Fuji F ( ) Dry to Dry 90'.

Comparing Samples 1 to 3 (invention) and Sample 4 (comparative example), the edges of Samples 1 to 3 are not transparent, so your eyes won't get tired even if you observe them for a long time, and the images will be clear because there is less flare. A song that shows that it will appear.

Heisei/2017/July>Entry into Japan Chief of Licensing Agency Lord

Claims (4)

[Claims] (1) A medical image forming method characterized by projecting a medical negative image on a CRT screen and directly photographing it on a reversal photosensitive material. (2) The medical image forming method according to claim 1, characterized in that the image on the CRT screen is photographed multiple times on one sheet of the photosensitive material while changing the image sequentially. (3) The medical image forming method according to claim 1, wherein the photosensitive material uses an internal latent image type silver halide emulsion that is not fogged in advance. (4) In claim 1, the photosensitive material has a thickness of 200 cm^.
A medical image forming method characterized by having an area of 2 or more.