JPH0359637A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material having good sensitivity and residual color property even in the case of ultra-rapid processing by incorporating a specific compd. into emulsion layers. CONSTITUTION:The gelatin content in the emulsion layers is in a 2.0 to 3.5g/m<2> range and the gelatin content in a protective film layer is <=0.9g/m<2>. The compd. selected from the compds. expressed by formula I, etc., is incorporated into the emulsion layers. In the formula I, Y1, Y2 respectively denote sulfur atom, selenium atom. There is, however, no case in which Y1 and Y2 are simultaneously the selenium atom. R1, R2 denote a lower alkyl group, alkyl group having a sulfo group. R denotes a lower alkyl group; A, B denote the nonmetal atom group necessary for perfecting a naphthothiazole ring, benzothiazole ring, etc.; X denotes anion; m denotes 1 or 0 and denotes m=0 at the time of an intramolecular salt. Thus, the degradation in the sensitivity, gamma, residual color, etc., is lessened even if the ultra-rapid processing is executed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material suitable for ultra-rapid processing.

[Conventional technology]

In recent years, the consumption of silver halide photographic materials has continued to increase. For this reason, the number of silver halide photographic materials to be processed has increased, and there is a demand for speeding up the development process, that is, increasing the amount of processing within the same amount of time.

The above trend can also be seen in the printing plate making field.

In other words, due to the rapid increase in the immediacy and frequency of information,
It has become necessary to perform printing plate-making work in a shorter time and in larger quantities. In order to meet the demands of the printing and plate making industry, it is necessary to simplify the printing process and
There is a need for faster processing of printing plate-making films.

Among them, newspaper companies in particular are making facsimile receivers faster in order to shorten the time it takes to publish a newspaper, but ultra-quick processing of receiving film has not yet been implemented. Therefore, there is an urgent need for rapid processing of such received films.

However, if the roller conveyance speed of an automatic developing machine is increased in an attempt to shorten the developing time for ultra-quick processing, a) the density will not be sufficient (reduction in sensitivity, contrast, and maximum density); b) Fixing, washing, drying, etc. are not performed sufficiently. Problems such as this arise. Insufficient fixing and water washing may cause changes in color tone during storage of the photosensitive material, leading to a decrease in image quality.

It also causes residual color due to pigments and dyes.

Among these problems, especially solving problem (a) above, 1
One method is to raise the temperature of the developer, but increasing the temperature may cause evaporation of the developer, resulting in sensitivity fluctuations due to concentration of the developer or water droplets adhering to the film insertion slot of an automatic processor. This causes problems such as uneven development.

In this specification, ultra-quick processing means that the leading edge of the film is inserted into an automatic developing machine, passes through a developing tank, a transition area, a fixing tank, a transition area, a washing tank, a transition area, and a drying area. [In other words, the total length of the processing line (m) is the line conveyance speed (m /
Processing in which the quotient (sea, ) ) divided by sea, ) is less than 60 seconds. The reason why the time for the crossing portion should be included here is that it is well known in the industry,
This is because the liquid from the previous process is swollen in the gelatin film even at the transition part, so it can be considered that the processing step is actually progressing.

[Purpose of the invention]

The purpose of the present invention is to achieve ultra-fast processing, e.g. a total processing time of 20 minutes.
It is an object of the present invention to provide a silver halide photographic material that solves the problems of the prior art as described above even when the processing time is 60 seconds, and has excellent working speed, high contrast, and good residual color.

[Structure of the invention]

As described above, the object of the present invention is to prepare a silver halide photographic material having at least one photosensitive silver halide emulsion layer and a protective film layer on a support using a roller type automatic processor for a total processing time of 20 minutes. In a silver halide photographic light-sensitive material that is developed in ~60 seconds, (1) the amount of gelatin in the emulsion layer is 2.
0 to 3.59/11", and (5) the amount of gelatin in the protective layer is 0.99/I11" or less, and (2) the emulsion layer contains the following general formula [I] or general formula (n ) This is achieved by a silver halide photographic material containing at least one compound selected from the compounds shown in (a).

General formula (1) [In the formula, Y represents a sulfur atom and a selenium atom, respectively. However, Y3 and Y are never selenium atoms at the same time. R1 and R2 represent a lower alkyl group and an alkyl group having a sulfo group, respectively.

R represents a lower alkyl group, and A%B represents a group of nonmetallic atoms necessary to complete the tothiazole ring, benzothiazole ring, naphthoselenazole ring, or benzoselenazole ring. X represents an anion. m represents 1 or 0, and in the case of an inner salt, represents m"0.] General formula (n) [However, in the above general formula, Z and z2 are a 5-membered ring and/or a 6-membered ring, respectively. represents an atomic group necessary to form a nitrogen-containing heterocycle. R1 and R4 each represent a saturated or unsaturated aliphatic group. Ql and Q represent 4-thiazolidinone, 4-imidazolidinone, 5- Represents an atomic group necessary to form a thiazolidinone or 5-imidazolidinone ring.L,
%L2, L, is a methine group, and Ll and R3, L, and R4
may be bonded to each other via a methylene chain to form a nitrogen-containing heterocycle. X represents a mineral acid or organic acid anion. n
! +n4 is 0 or 1; represents an integer of 1. ] Details of the present invention will be described below.

The dye represented by general formula (1) in the present invention will be explained.

In general formula (1), Yl and Y represent a sulfur atom and a selenium atom, respectively. However, %Yl and Y do not represent selenium atoms at the same time.

A and B each represent a group of nonmetallic atoms necessary to form a benzothiazole ring, a benzoselenazole ring, a naphthothiazole ring, and a naphthoselenazole ring, and these heterocycles are lower alkyl groups, alkoxy groups, and hydroxyl groups. ,
It may be substituted with an alkoxycarbonyl group, a halogen atom, or a hydrogen atom. Note that the lower alkyl group may be substituted. R, , R, are each a lower alkyl group,
Represents an alkyl group having a sulfo group or an alkyl group having a carboxyl group. R represents a methyl group, an ethyl group, or a globyl group. X represents an anion commonly used in cyanine dyes, such as a halogen ion, a benzenesulfonate ion, and a p-F luenesulfonate ion.臘 is ■
Or it represents O, and when it is an inner salt, it represents m-0.

Next, specific examples of the sensitizing dye represented by the general formula (1) will be shown, but the invention is not limited thereto. The sensitizing dyes used in the silver halide photographic material of the present invention can be easily synthesized by referring to U.S. Pat. I can do it.

-1 -2 -3 -4 -5 ■ 6 I-7 ShiH3 -8 -9 ■ 0 ■ i -12 -13 -14 ■-15 -16 -17 -18 9 ■-20 ■-21 ■-22 ■-23 ■-24 ■-25 ■-26 ■-27 D-28 ■-29 )υ3N Ze so,e Next, general formula (n) will be explained.

In the general formula (II), Zl and Z each represent a 5-membered ring and/or
Or represents an atomic group necessary to form a 6-membered nitrogen-containing heterocycle. A substituent that does not adversely affect sensitization may be attached to the carbon atom of this heterocycle.

Examples of this heterocycle include thiazoline ring, thiazole ring, benzothiazole ring, naphthothiazole ring, selenazole ring, benzoselenazole ring, naphthoselenazole ring, oxazole ring, benzoxazole ring, naphthoxazole ring, 2-quinoline ring, 4 -Quinoline ring, 2-pyridine ring, 4-pyridine ring, 3.3-dialkylindolenine ring, benzimidazole ring, etc., with a halogen atom, an alkyl group, an alkoxy group, a hydroxy group located between the carbon atoms of this heterocycle , a substituent such as a monoaryl group may be attached.

R1 and R4 are each a saturated or unsaturated aliphatic group, such as a lower alkyl group (having 8 or less carbon atoms), a substituted alkyl group (
Preferably, the alkyl group radical has 5 or less carbon atoms)
represents. Qi and Q represent atomic groups necessary to form 4-thiazolidinone and 4-imidazolidinone.

Examples of the substituent attached to the nitrogen atom at the 3-position of thiazolidinone or imidazolinone include an alkyl group,
Examples include an allyl group, an aralkyl group, an aryl group, a hydroxyalkyl group, a carboxyalkyl group, and an alkoxycarbonylalkyl group.

Ll+L! and L3 may be a methine group or a substituted methine group, and R, L, and R1 may each be bonded to each other via a methylene group to form a nitrogen-containing heterocycle (eg, 5-membered, 6-membered, etc.). n3+n4 each represent O or l. When 0, the dye forms a betaine structure.

X represents a mineral or organic acid anion such as chloride, bromide, iodite, verchlorate, benzenesulfonate, p-toluenesulfonate, methylsulfate, ethylsulfate, and the like.

Next, the general formula used in the present invention () Inverts the sensitizing dye.

However, this is the sensitizing dye. ■ ■ ■ to de ■ ■ ■ to de ■ ■ ■ de ■ -10 ■ 11 ■ 12 ■ 13 ■ 14 ■ 15 − ■ 16 ■ 17 ■ 18 de ■ 19 20 ■ 21 de − ■ -22 ■ 23 ■ 24 ! ! ■ =25 ■ 26 ■ 27 2Hs C211゜ ! − ■ ■ 28 ! − ■ 29 CI, CI, COO- ■ 30 C112C112CH2CI (2SO311■ 31 ■ 32 ■ 33 one ■ -34 ■ 35 ■ 36 ■ 37 ■− ■ 38 C.II.

CI! .

C, 11° - To use the compound represented by the above general formula CI) [1) in a silver halide emulsion, it can be added and dissolved in a coating solution, or it can be added and dissolved in water or an organic solvent such as methanol, ethanol, or acetone alone. Also, < may be added by dissolving a mixed solvent thereof. However, if necessary, it can also be added to layers adjacent to the silver halide emulsion layer, such as a protective layer and an intermediate layer, to the extent that it does not affect photographic performance.

The amount of the compound used in the present invention when added to a silver halide emulsion varies depending on the type of silver halide emulsion and the type of compound, but is usually in the range of 5 mg to 1000111 g per mole of silver halide.

The silver halide emulsion used in the light-sensitive material of the present invention includes conventional silver halide emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Any commonly used silver halide grains can be used, and the silver halide grains may be those obtained by any of the acid method, neutral method, and ammonia method.

The gelatin used in the present invention may be any gelatin treated with acid or lime. In addition, one or two types of hydrophilic colloids such as gelatin derivatives, gelatin and other polymer graft polymers, other proteins, sugar derivatives, cellulose derivatives, synthetic hydrophilic polymer substances such as single or copolymers, etc. It can also be used in combination. In the present invention, the amount of gelatin in the emulsion layer is 2
．． 0 to 3.59/m2", preferably 3.09/11"
The amount of gelatin in the protective film layer is 0,9y/-
Below, it is preferably 0.859/m2''.

The silver halide grains may have a uniform distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside and the surface layer of the grain, and the m-image The particles may be formed mainly on the surface, or may be formed mainly inside the particles.

In the process of grain formation and/or growth, silver halide grains are produced by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts. Metal ions are added using at least one selected from salts (including M salts), and metal ions are added inside the particles and/or
Alternatively, these metal elements can be contained on the particle surface, and reduction sensitizing nuclei can be provided inside the particle and/or on the particle surface by placing the particle in an appropriate reducing atmosphere. Particularly in the present invention, since it is preferable that the photosensitive material is exposed to high intensity light, it is preferable that the photosensitive material contains an iridium salt or a complex salt.

Any shape of the silver halide grains according to the present invention can be used. One preferable example is a cube having (1001 plane) as a crystal surface.

Also, U.S. Patent Nos. 4,183,756 and 4,225.6
No. 66, JP-A-55-26589, JP-A-55-42
737, etc., and The Journal of Photographic Science (J, Photgr, S
Particles having shapes such as an octahedron, a tetradecahedron, a dodecahedron, etc. can be prepared by the method described in the literature such as 21.39 (1973), and used. Furthermore, particles having twin planes may be used.

The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes.

Also, any grain size distribution may be used, and emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (referred to as monodisperse emulsions) may be used. They may be used alone or in a mixture of several hundred. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

Although the photosensitive silver halide emulsion can be used as a so-called Pria+1tive emulsion without chemical sensitization, it is usually chemically sensitized.

For chemical sensitization, 1afkides or Ze
The book by l i kman et al. or H. Fr1eser
! D
ie Grundlagender Photogra
phischen Prozessa with 5il
berhal.

Geniden, Akademicche Verl
agsgesellschaft.

(1968) can be used.

That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or activated gelatin, a reduction sensitization method using a reducing substance, a gold or other noble metal compound, or a combination of these methods can be used. .

As the photosensitive emulsion, the above emulsion may be used alone,
Two or more types of emulsions may be placed on the stand.

When carrying out the present invention, for example, 4-hydroxy-6-methyl-1,3,
Various stabilizers can also be used, including 3a,7-titrazaindene, 5-mercapto-1.phenyltetrazole, and the like.

Furthermore, if necessary, a silver halide solvent such as thioether,
Alternatively, a crystal habit control agent such as a mercapto group-containing compound or a sensitizing dye may be used.

In the emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

The photosensitive material of the present invention may further contain various additives depending on the purpose. These additives are described in more detail in Research Disclosure Vol. 176, 1 tem.
17643 (December 1978) and Volume 187 I
temH1716 (November 1979), and the relevant parts are summarized in the table below.

Additive types RD 17643 RD 18716 1, Chemical sensitizers 23 pages 2, Sensitivity enhancers 648 pages right column Same as above 46 Brighteners 24 pages 7, Stain inhibitors 25 pages right column 8, Dye image stabilizers 25 pages 9, Hardener
26 pages 10, binder 26 pages 1
1. Plasticizers/Lubricants Page 27 12 Coating aids/Surface active agents Pages 26-27 13. Static inhibitors Page 27 In particular, the silver halide emulsion contrast enhancing or development accelerating alkylenoxacite or its compound of the present invention, Derivatives of amines, etc., tetrazo, page 650, left to right column, page 651, left side, same as above, 650, right column, same as above, for the purpose of increasing sensitivity, polymonocytyl, nistylium compounds, hydrazine compounds, thioether compounds, thiomorpholines, 4 It may also contain class ammonium compounds, urethane derivatives, urea derivatives, imidazole derivatives, and the like.

In carrying out the silver halide photographic material of the present invention, for example, the emulsion layer and other layers can be constructed by coating on one or both sides of a flexible support commonly used in photographic materials. Useful flexible supports include films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acid mmm, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or a-olefin polymers. (
Examples include paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer, or the like. The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion with emulsion layers and the like. The undercoating treatment is as per JP-A-52-104913 and JP-A-52-104913.
No. 9-18949, No. 59-19940, No. 59-1
The treatments described in each publication of No. 8949 are preferred.

In the silver halide photographic light-sensitive material according to the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used.

As for the exposure time, in addition to normal exposure of 1/1000 to 100 seconds, short-time exposure of 1/10' to 1/10'' seconds can be applied with xenon 7-lash, cathode ray tube, or laser light.

After exposure, the silver halide photographic light-sensitive material of the present invention has the following properties:
It is processed in an automatic processor with a total processing time of 20 to 60 seconds. The developer used during processing is an alkaline solution containing a developing agent such as hydroxybenzenes, l-phenyl-3-pyrazolidones, aminephenols, aminobenzenes, and the like. However, alkali metal salts such as sulfites, bisulfites, bromides, and iodides can be included.

〔Example〕

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Example-1 (Preparation of emulsion) Solution A Water
9.7a Sodium chloride 2
0 g gelatin 105
g solution B water
3.8m12 Sodium chloride
380g gelatin 94
g Potassium bromide 420 g 0.10% aqueous solution of hexachloroiridate potassium salt 28 raQ
0.001% aqueous solution of potassium hexabromorodate salt 1. omQ
Solution C water
3.8m12 silver nitrate
1700 g in the above solution A kept at 40°C,
While maintaining pl+ at 3 and pAg at 7.7, add the above solution B.
and solution C simultaneously over a period of 60 minutes;
After stirring for an additional 10 minutes, the pH was adjusted to 6.0 with an aqueous sodium carbonate solution. s, 20% aqueous magnesium sulfate FfI22 and 5% aqueous polynaphthalene sulfonic acid solution 2.55α were added, the emulsion was cured at 40°0 for 70 minutes, decanted, and washed with water to remove excess salts from the aqueous solution. do. Next, 3.7Q of water was added to it to disperse it, and again 0.9a of 20% magnesium sulfate aqueous solution was added.
to remove excess salt from the aqueous solution in the same manner.

Add 3.7Q of water and 141g of gelatin to it,
Disperse for 55°030 minutes. This allows bromide #13
5 mol% of silver chloride, 65 mol% of silver chloride, and a monodispersity of 9 with an average grain size of 0.25μ are obtained. Here, the monodispersity is a value expressed by 100 times the standard deviation of particle diameter divided by the average particle diameter.

120 mff of 1% citric acid aqueous solution, 5 potassium bromide
% aqueous solution was added to the emulsion adjusted to pH 5.0 and pAg 7, and 120 ml of a 0.1% aqueous solution of I.lium thiosulfate and 80 ml of a 0.2% chloroauric acid aqueous solution.
2 and ripened at 60°C to achieve maximum sensitivity.

Compound 1-722-5 was added to the above emulsion as an antifoggant.
-7tsQ 0.5% solution of mercaptotetrazole.

30 mQ of 10% solution of hydroquinone, 12On+Q of 5% aqueous solution of potassium bromide, 1.3.3a of 4-hydroxy-6-methyl as a stabilizer, 180 m4 of 1% solution of 7-titrazaindene. Gelatin lθ% aqueous solution 200
After adding m1 to stop the ripening, the above emulsion was divided into IO equal parts, gelatin solution was added to each part to adjust the amount of gelatin to various levels, and then sensitizing dyes were added as shown below.

After adjusting the pH and pAg, add 50 mL of a 10% solution of hydroquinone as an antifoggant, 19a + 20% saponin aqueous solution as a spreading agent, and 50 mL of a 4% aqueous solution of styrene-maleic acid polymer as a thickener. 30g of high molecular weight polymer latex of ethyl acid;
After 1 hour and 20 hours, l-hydroxy-3,5-dichlorotriazine sodium salt and formalin were added as hardening agents, and the emulsion was coated on a subbed polyethylene terephthalate support with silver 3.89/10. Furthermore, as a protective film, 100ml of a 10% potassium bromide aqueous solution was added to an aqueous solution of 500g of gelatin, and as a spreading agent, 1% of 1-decyl-2-(3-isopentyl)sacunnate-2-sulfonate sodium was added. Add 400+++Q of aqueous solution, add and disperse 100g of amorphous perilla with an average particle size of 3.5μ, and gelatin is 1.h/ff1
The emulsion layer and the protective layer were coated at the same time in such a manner that they were coated at the same time.

In order to determine the sensitivity of the sample obtained in this way, halftone exposure (exposure through a return screen) was performed at 1/100,000 seconds using a xenon light source and a Wratten filter No. 88A (
(manufactured by Kodak) and processed with a roller automatic developing machine using a developer and fixer having the following composition. During the processing, the total processing time was varied by changing the transport speed of the film. Detailed processing conditions are shown below.

Processing conditions Development: 38℃ 25 seconds 12.5 seconds fixing
30℃ 25 seconds 12.5 seconds Washing with water Room temperature 20 seconds 10 seconds drying 45℃ 20 seconds 10 seconds Rapid feed speed 1450 II m/win 2900 mm/win Total processing time 90 seconds 45 seconds Developer formulation Pure water (ion exchange water) Approx. 800 mQ Potassium sulfite 60 g Ethylenediaminetetraacetic acid disodium salt 2 g Potassium hydroxide 10.5 g 5-methylbenzotriazole diethylene glycol 25 g 1-phenyl-41-dimethyl-3-pyrazolidinone 300 B 1-phenyl-5-mercaptotetrazole 60 ag bromide Potassium 3.5 g Hydroquinone 30 g Potassium carbonate] and 5 g pure water (ion exchange liquid water) were added to make a final volume of 1,000 mα. The developer pl+ was 10.8.

Fixer formulation (composition person) Ammonium thiosulfate (72.5% W/V aqueous solution) 240 va
n Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g
Acid 6g Sodium citrate dihydrate 2g Acetic acid (90%
W/V aqueous solution) 13.6aQ (Composition B) Pure water (ion-exchanged water) 17ml Sulfuric acid (90% W/V aqueous solution) 4.7g aluminum sulfate (i, O, equivalent content is 8.1% W/W) aqueous solution)26.
5g When using a fixer, add the above composition A1 to 500I1112 water.
They were melted in the order of composition B, finished to IQ, and used.

The pH of this fixer was about 4.3.

Sensitivity, density, fog, and gamma values were determined for the images obtained by the above processing. Sensitivity is the reciprocal of the exposure amount required to obtain a density of 3°O for sample No.

The relative sensitivity is shown with l being 100. Also, the gamma value is
It is shown by the slope of the straight line connecting the points of density 0.3 and density 3.0 on the photographic characteristic curve. The photographic performance was evaluated according to a 5-point scale, with 1 indicating no use at all, 2 indicating a level that may cause problems, 3 indicating the lower limit of use, 4 indicating a level with no problems, and 5 indicating a good level.

As can be seen from the results in Table 1, ultra-rapid processing deteriorates sensitivity, gamma, and residual color under comparative conditions, but with the groove bottom of the present invention, all values are reduced by standard processing (38°C, 25 seconds).
It became clear that the same performance could be obtained.

〔Effect of the invention〕

With the present invention, even with ultra-rapid processing, sensitivity, gamma,
It is our great endeavor to provide a silver photographic light-sensitive material that exhibits minimal deterioration such as residual color.

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one photosensitive silver halide emulsion layer and a protective film layer on a support is processed in a roller type automatic developing machine in a total processing time of 20 to 60 seconds. In the silver halide photographic light-sensitive material to be developed, [1] the amount of gelatin in the emulsion layer is in the range of 2.0 to 3.5 g/m^2, and the amount of gelatin in the protective film layer is 0.9 g /m^
2 or less, and [2] the emulsion layer contains at least one compound selected from the compounds represented by the following general formula [I] or [II]: . General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Y_1 and Y_2 represent sulfur and selenium atoms, respectively. However, Y_1 and Y_2 are never selenium atoms at the same time. R_1 and R_2 represent a lower alkyl group and an alkyl group having a sulfo group, respectively. R represents a lower alkyl group, and A and B represent a nonmetallic atom group necessary to complete the naphthothiazole ring, benzothiazole ring, naphthoselenazole ring, or benzoselenazole ring. X represents an anion. m represents 1 or 0, and when it is an inner salt, m=0. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. Represents a group of atoms. R_3 and R_4 each represent a saturated or unsaturated aliphatic group. Q_1 and Q_2 represent 4-thiazolidinone, 4-imidazolidinone, 5-thiazolidinone, or an atomic group necessary to form a 5-imidazolidinone ring. L_1, L_2, L_3 are methine groups, and L_
1 and R_3, and L_3 and R_4 may be bonded to each other via a methylene chain to form a nitrogen-containing heterocycle. X represents a mineral acid or organic acid anion. n_3, n_4 are 0 or 1
represents an integer. ]