JPS6188254A - Structural body for photothermography - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to silver halide color photothermographic structures. In other words, the present invention relates to a two-color or three-color separation photothermographic complete recording system that utilizes a particular class of leuco dyes as color formers.

Photothermographic imaging systems are materials that form images when exposed to imagewise light and then heated. photoactivation or photoactivation of the components, and subsequent heating causes both imaging reactions to occur differently in the exposed and non-i'-exposed areas.

RT+41 (TD forming material for halo r/chemical steel photothermography has been known for a long time. The image-forming material consists of a non-photosensitive reducible silver source, a photosensitive material that produces silver upon irradiation, and a reducing agent for the silver ions in the silver source.The photosensitive material is generally a photosensitive silver halide. , and it must be in catalytic proximity with the non-photosensitive silver source. Catalytic proximity means that these two materials are in such a way that the reduction of silver can be catalyzed by the parent nuclei formed on the silver halide. When silver halide is exposed to light, a small raster of silver atoms is produced.

The imagewise distribution of these clusters is known as the latent image. This a-image is generally not visible by conventional means and the photosensitive product must be further processed to form a visible image. As mentioned above, visible light 1y is generated by the contact of koji ions in the catalytic vicinity of the latent image nucleus.

The silver sources used in this technical field contain γ atoms, which are the substrates for silver ions. The early and still preferred sources generally consisted of silver salts of carbonaceous carboxylates having from 10 to 60 carbon atoms. 41. of behenic acid or a mixture of acids containing acetic acid. The I salt is mainly used. Salts of other organic acids or other organic substances such as imidazolates have also been proposed, and U.S. Pat. No. 4,260,677 describes the use of inorganic or organic salt complexes as image source materials. Disclosed.

Chromogenic "dry silver" image forming systems are well known in the art. Color development is based on an oxidation/reduction reaction at elevated temperatures between an exposed fatty acid silver salt that has been halogenated and dye-sensitized to a specific wavelength and a color developer. For example, U.S. Pat. No. 3,531,286 teaches containing a QP coupling component of a p-phenylenediamine developer and a phenol or active methylene coupler in close proximity to a light-sensitive emulsion. are doing. J, W, Carpenter and P, W, Lown's Research Disclosure A17029, published in June 1978, is a photothermographic type halonized f'! This is a review of prior art related to the system.

U.S. Pat. No. 4,021,240 discloses the use of a nulfonamide phenol reducing agent and a 4-identical photographic color coupler in a thermographic or photothermographic emulsion to form dye images, including polychromatic images. It is disclosed that

U.S. Pat. No. 3,985,565 discloses the use of a particular class of phenolic type four-way color couplers in photothermographic emulsions to provide a family of colors.

U.S. Pat. No. 4,021,250 describes a photothermographic system consisting of a salt, a catalytic amount of photosensitive silver halide, a reducing agent, and a binder as a shelf life extender.
The use of 025% leucothiazine dye is disclosed. The example disclosed therein used 1.87% chlorothymol and 0.126% phthalazinone as the imaging reactants.

It is known that leucomethylene del-thiazine dyes are effective against the Kama type. U.S. Patent No. 2.646.3
No. 67 discloses, for example, a carbinelesscopy system using benzoylleucomethylene blue as a color intercolorant. US Pat. No. 3,447,944 discloses a thermographic Eco system that utilizes leucomethylene blue and its derivatives as coloring agents. U.S. Pat. No. 4,309,255 relates to leucomethylene blue in electrochromic recording paper.

#:f Curve Publication No. 59-5239 discloses a two-sheet type positive-acting photosensitive heat-developable diffusion transfer structure.

SUMMARY OF THE INVENTION Briefly, the present invention comprises photosensitive and non-photosensitive S sources;
Optional silver halide, a binder, an oxidizable leucofenazine or phenoxazine or phenothiazine dye, and carvone 1'v as a development accelerator! or a single sheet negative-acting photothermographic construction comprising a photosensitive chromogenic element consisting of a Lewis acid or a delanested acid on a supporting base. Known oxidizable leucofenazine or phenoxazine or phenothiazine are effective in the present invention. Butyric bodies can have colors ranging from blue-green to yellow.

The photothermographic portion of the element is photosensitive and preferably between 150 and 650"F' (about 65 and 180C).
It is sufficient that the circular image forming property jt4 ($ number or axis number) is developable by being heated to a range of * (for example, with a heated drum roll or by infrared exposure).

Particularly important are silver halide in the binder,
A silver halobide photothermographic system consisting of a silver source substance in catalytic proximity to the silver halide and a reducing agent for silver ions; these systems are commonly known as "dry silver" compositions. . This '4 system may have a single layer or multiple layers, as is well known.

The chromogenic elements of the present invention can be of two colors or can be used in a 1.26 resolution photothermographic recording system.

In such systems, it may be necessary to provide a "barrier layer" within the topcoat layer that is impermeable to the upper adjacent collar layer. Such structures are described, for example, in US Pat. No. 1). Nos. 460,681 and 4,452
, No. 883.

In this application, "leuco dye" means a colorless or slightly bound dye that can be oxidized to a colored body; "aryl" means phenyl or naphthyl; "arylene" means phenylene or naphthylene; "Lower alkyl" means alkyl having 1 to 4 carbon atoms; "lower alkoxy" refers to alkoxy having 1 to 4 carbon atoms; "aliphatic" means alkyl having 1 to 4 carbon atoms; "aliphatic" means alkyl having 1 to 4 carbon atoms; "halocarbon" means fluorine, chlorine, bromine, or iodine; and "in combination with" means in the same place as or in an adjacent path to It means that. For example, the location of the photosensitive silver halide in the otothermographic elements or compositions of the present invention is such as to enable catalysis. Accordingly, the photosensitive halobinated steels described are compatible with the described oxidation-reduction imaging formulations (Tang J
r consisting of a complex salt such as silver behenate or silver stearate (= converting agent, reducing agent of the present invention, and phenomenon modifier)
may be present in the same layer or in an adjacent layer.

Details The present invention provides a support paste containing a silver source, a silver halide of Renjun°, a leuco dye as a reducing agent for the ions,
a) a leuco dye of the formula [wherein X is -8-1-o-1 or - NO-; each B may be the same or different and individually represents 1) halogen, 1)) unsubstituted aryl or alkyl group, or alkyl, alkoxy, cyano, hydroxy, halogen, nitro, Mercapto, alkylsulfonyl, arylsulfonyl, such groups substituted with up to 4 groups selected from mercapto, alkylsulfonyl, arylsulfonyl (Z is as defined below), provided that each alkyl and alkoxy group is 1 to 20 carbon atoms, preferably lower alkyl and alkoxy, and 1ii) , 1)) an unsubstituted aryl or alkyl group, or selected from alkyl, alkoxy, cyano, hydroxy, halogen, nitro, mercapto, alkylsulfonyl, arylsulfonyl, and Z, where 2 is as defined above R ' may be the same or different and are individually selected from hydrogen, halogen, alkyl or alkoxy of 1 to 6 carbon atoms, or their subgroups partitioned with up to 6 halogen atoms. L is 2 or hydrogen; with the proviso that R and L together can contain up to 5 carbonyl and sulfonyl groups; and b) a phenazine, phenothiazine, or phenoxazine leuco dye; The development accelerator has i) formula % formula %) (wherein n is an integer with a value of 1 to 4, preferably 1 to 6, and R10 is unsubstituted or amino, hydroxyl, aryl,
lower alkyl, lower alkoxy, cyanogen, sulfonyl,
is a group substituted with at least one group selected from mercapto, nitro, halogen, and Z (where Z is as defined above); however, when n is 1, Rlo is a group having up to 10 carbon atoms. , alkyl, alkenyl, 71J-, oyohyphenylalkyl, and when n is 2.6, or 4, R10 is a group consisting of alkenylene, alkylene, and arylene of up to 14 carbon atoms. 1)) Lewis acids preferably carried from halides, nitrates, sulfuric IL sulfonates, and carboxylic acid groups, such as ammonium nitrate, alkylammonium nitrate, N
i) Zn, kl, Cu, and Hg nitrates, sulfuric acid chlorides, etc.; and iii) derenestezic acids preferably selected from sulfonic acids, sulfinic acids, phenols, phosphonic acids, phosphinic acids, and sulfimides. It consists of one type even if it does not contain acid.

The leuco dye can have a molecular weight of up to 2000 (preferably up to 700) and the carboxylic acid can have a molecular weight of up to 500 (preferably up to 400).

A preferred photothermographic composition of the present invention is “
It is of the ``Rice Silver'' type.

A chromogenic element capable of providing an image ranging from cyan to yellow (including magenta, red, violet, purple, and blue) can be of a single configuration, and
The photosensitive layer may be combined with a leuco dye, that is, it may have a two-layer structure. The single layer construction must contain the silver source material, silver halide, developer, and development accelerator in each layer. 21? In the j construction, the photosensitive layer has a topcoat layer consisting of a leuco dye and an acid material.

The dry silver two layer construction must contain a silver source and 1μ of halide in one emulsion layer (usually the layer adjacent to the substrate). Other components may be present in the same layer, a second layer, or both layers.

Rendong's additives include rolling agents, coating aids, and other aids.

The photothermographic color assembly of the present invention contains at least one of the spectrally sensitized chromogenic elements of the present invention to create a tabletop or multicolor photothermographic color recording system. Spectral sensitization in the presence of at least two chromogenic elements is characterized in that each chromogenic element is directed to a spectral range that differs by at least 60 nm from the other chromogenic element, and each chromogenic layer is Any two of the following colors, such as black, yellow, red, green, blue, and purple, as long as they produce a visible dye that has an absorption maximum that differs by at least 60 nm from the absorption maximum of the dye placed in the chromogenic element. It only needs to be for one pair of colors. Preferred color pairs to which the composition may be spectrally sensitized are yellow/cyan, yellow/magenta, and cyan/magenta. Preferably, a barrier polymer is provided between each pair of color forming layers that is impermeable to the solvent system of the upper color component. Such barrier polymer(s) are essential to achieve the desired color separation. The test to determine if the barrier polymer is impermeable to the next layer's solvent is f? ij can simply be done. Such a test is described in U.S. Patent No. 4.45.
No. 2.883, and this patent is an unknown reference. The photothermographic color construction may be constructed from six separate monochromatic layers to provide a six color system.

The additional oxazine and thiazine leuco dyes used in the present invention can be produced by acrylating unsaturated phenoxazine or phenothiazine compounds to N-acrylated phenoxazine or phenothiazine compounds, as is known. As is known, nitration in acetic acid gives the 6,7-sinitrophenoxazine or phenothiazine compound after recrystallization. # by Platinum Metal! A mediated hydrogenation yields the corresponding diamino compound. Treatment of the diamino compound with a suitable alkylating or acylating agent in the presence of a copolymer such as C-lysine, triethylamine or sodium hydroxide at room temperature provides a diamino-substituted leuco dye.

To prepare the leucophenazine dye useful in the present invention, a phenylene diamine compound such as N,N-dimethyl p-phenylene diamine and an aniline compound +! :1
For example, N,N-dimethylaniline is mixed in a solvent, preferably water, in a reactor and stirred, preferably at room temperature. Preferably, the reaction is carried out in an acidic aqueous cycloreduction. A second aniline compound, such as 4-methylaniline, is then added to the mixture. Then, the resulting mixture
The mixture is stirred and heated for a sufficient period of time to form the dye product in free form. Ionizable halide salts in solution such as KI
, NaCl is added to precipitate the dye product. The solution is then cooled and the dye is collected by filtration and air dried. Hydrogen leuco dyes are obtained by reduction in water in the presence of a water-soluble reducing agent such as sodium dithionate. Leuco dyes are obtained by extraction with a non-reactive water-insoluble solvent (eg methylene dichloride) and treatment of the organic phase with a reactive halide compound (eg benzoyl chloride).

In preferred embodiments in which the photothermographic construction is of the Dray Silver type, the silver source material may be any material containing a reducible source of scissor ions, as described above. Silver salts of organic acids, especially long-chain (10 to 60 carbon atoms, preferably 15 to 28 carbon atoms) fatty carboxylic acids, are preferred. Complexes of organic or free silver salts in which the ligand has a large stability constant of 4.0 to 10.0 with respect to the ion are also desirable. The silver source substance is present in the cambial layer approximately 5 to 70 minutes.
It should constitute % electric buds, preferably 7-30% by weight. The second layer in a two-layer construction will not affect the silver source material damage required in single-imaging applications.

The silver halide may be any photosensitive silver halide such as silver bromide, silver iodide, silver chloride, silver bromoiodide, silver chlorobromoiodide, silver chlorobromide, etc., and it is used as a silver source material. Catalyst proximity state Kl
It may be added to the emulsion layer in a q manner such as 'l+'.

The halogenated rust is generally present as 0.75 to 15% by weight of the imaging layer, although larger amounts up to 20% or 25% are also effective. It is preferable to use 1 to 10% silver halide in the image forming layer, and 1.5 to 7%.
Most preferably, 0% is used.

If the composition has more than one color-forming element, the dye produced from the leuco dye in each color-forming layer should of course be different. Maximum absorbance in reflection or transmission is at least 6
A difference of 0 nm is required. Preferably the absorbance maxima of the resulting dyes differ by at least 80 or 1)00n. If three types of dyes are to be produced, two of them
The two dyes should differ by at least this minimum, and the sixth dye should differ from at least one of the other dyes by at least 150 nm, preferably at least 200 nm or at least 250 nm.

This results in a good full color gamut final image.

In the present invention, a reducing agent (developer) for the ion
is the above-mentioned leucophenazine or phenoxazine or phenothiazine dye, which contributes ions to the metal steel and itself becomes a colored dye. A number of representative examples of these dyes are shown in Tables 1 and 2. Hygiene agent is 0.1 to 10i of the image forming layer! It should be present as i amount %.

In two-layer constructions, a slightly higher percentage of 2-15% tends to be more desirable when the reducing agent is in the second layer.

Additional reducing agents may be useful. Regular photographic chemicals like phenidone, hydroquinone and catechol! i4
J is useful in small amounts, and a hindered phenol reducing agent may also be added. Leuco dyes other than those specified above (eg, crystal violet) may be useful as additional reducing agents in small amounts (up to about half the amount of primary reducing agent).

Although known toning agents such as phthalazinone and phthalazine are not essential to the construction, they are desirable.

These substances may be present in amounts of, for example, o, o o i to 1% by weight.

Binders for silver binding include gelatin, polyvinyl acetal,
Polyvinyl chloride, polyvinyl acetate, I! ¥: Acid cellulose, ethyl cellulose, polyolefin, polyester, polystyrene, polyacrylonitrile, polycarginate, methacrylate copolymer, maleic anhydride copolymer, butadiene-styrene copolymer, etc. σ
) is derived from well-known foreign and synthetic resins such as When using multiple IB1 temporary 4Ck, the binder should be selected to match the bath salt used. Of course, copolymers and terpolymers including the above-mentioned binders are included in the formulation.

A preferred high content binder for photothermography is polyvinyl butyral. Binders are generally used in the range of 20-75% by weight of each layer, preferably 60-55% by weight.

Symptom modifiers that may be useful in the present invention have been previously determined. The acid selected for a particular photosensitive element depends on the activity of the leucodiazine, oxazine, or thiazine dye;
That is, it depends on how easily the colored body ages. Leuco dyes that are highly reactive require less sulfuric material than leuco dyes that are less easily oxidized. For example, if the par is a script
Turquois™ (a more reactive leuco dye) requires phthalic acid, while Cobichem ■ (a less reactive leuco dye) requires a more reactive acid such as 4-nitrophthalic acid. Representative preferred development modifiers include phthalic acid, benzoic acid, chlorinated and nitro-substituted benzoic acids, 1,2,4-benzenetricarzanyl[, 2,3-naphthalene dicarzenic acid, tetrachlorophthalic acid, 4-methylphthalic acid, homophthalic acid, 4-nitrophthalic acid, 0-
Aromatic carboxylic acids and their anhydrides such as phenylacetic acid, naphthoic acid, naphthalic acid, phthalic anhydride, naphthalic anhydride, tetrachlorophthalic anhydride, 3-nitrophthalic acid; malic acid, chloroacetic acid, idaconic acid, tartaric acid, aliphatic carmenic acids such as benzoylformic acid, thioniacetic acid: bransted acid, e.g.
2, phenol such as 4-dinitrophenol, 2,6-dinitrophenol and pentachlorophenol,
Other sigma substances such as sulfimides (eg saccharin); or Lewis acids including nitrates such as nickel nitrate, copper nitrate, mercury nitrate, zinc nitrate, aluminum nitrate, ammonium nitrate.

Sensitizing dyes useful in the present invention include a number of known compounds, as well as erythrosine (synthesized as in U.S. Pat. No. 2,493.748), erythrosine (manufactured by Aldrich Chemical Co., Milwaukee, Wis.) Rice (Synthesized as in No. 719,495, No. 719,495) (Synthesized as in No. 3,719,495).

The supporting base or substrate is a transparent or opaque composite film. Preferably it is comprised of materials such as polyesters (e.g. polyethylene terephthalate), cellulose esters (e.g. vinegar, cellulose butyrate, cellulose acid propionate), polyolefins, polyvinyl resins and the like.

The fracture can be formed as a single layer, for example by knife coating or extrusion, and dried before the next layer can be applied.
It is also possible to produce two copies of each monochrome, for example by double slide or double extrusion: i.e.
Each sensitized silver layer can be co-coated with its respective topcoat (which may contain a barrier resin), thereby reducing the number of coater cuts.

Representative examples of useful leucodiazine, oxazine, and thiazine dyes are given in Tables 1 and 2 as Dm for two-layer elements prepared as follows. and DInaX are shown together.

Kinkyu Jun Behe 7sho Bank 1.71! Toluene: 9.31 Methyl ethyl ketone (MEK): 3.1 g These six components were homogenized. The following were added to it separately: Toluene 71.1.9 Ethanol 6.51 Mixing was continued until the Butpal was dissolved. Then ZnCl24.
A solution of 3 g dissolved in 1 QQm of ethanol was added and mixing continued for 1 hour. This dispersion was coated with a knife coater through a 76μ (3 mil) orifice (wet thickness).
Sou 7 ('-force 1.yder treatment 69)
(Vicksburg, I). The coating film is 85
Dry for 4 minutes at 185"F'.

Ethanol 50.0.9 Acetone 42.5 g Butpal E'-767,5# Phthalic acid 0.5 g The five components were mixed until dissolution occurred. To individual samples (8 g) of this top coat solution, 0.05 # of each of the leuco dyes listed in Tables 1 and 2 were added and mixed. Each sample was applied with a pad applicator to 76 μ (6
Mill) applied in wet thickness. These constructs were prepared at room temperature (21
°C) for 15 minutes (condition A) or 85 °C (185”
These constructs were exposed to approximately 3800 fc for 20 seconds with a 3ν model 666 tungsten lamp and then heated to 1246 C (255 ff) with a heating blanket 7° processor.
Developed for the specified time.

1st - RI
A 10”H Magenta [1,090,28
A 10”H Akasou High A I
04 ◎)◎ CH3CH2CF3 CH,CH
, C.F.

5 ◎ CH3CH2CF3 CH3C)!
, C'F36 ◎ CH3CH2CF3
CH3CHpCFz7QC2H5C)13CH2CF,
C)! , CH2CF38 ◎mlJ, 0M3
CH? CF3CH3CH, CF.

°　　　. 2゛”°　°“°　°“′°°”.

i Q QxCj, CH3CH3CH7
C)! 51) 0 C) (3CH3CH3
CH3CH3 machiner (1,170,19A
60CH3 master 0.56 1.21
A, 10H magenta 0.82 1.31
A IDC)-13 Red #0.4
30.96 F! 3000H, Masentor l'1.55 2.55 A 10Q
C) (3 red purple 0.21 1.02 A
90CH3: V1 Mi Wi, 051.92
A 5CH3 red purple rl, 581. F1
4A 9°/Del RI
R) R3F,, R5” 165
°C (275 strokes) Mouth 1) 6”0 (240 below) φ ＋tnHsu [everyone 1); 1 R6 color Dmin D-nax '(item (t'p) CH3 red purple 0.6F+ 1
．． 8F! AOCH3 red purple D, 301.51
A 20 CH5 red purple 0.21)
[1,58B 21/24￥ O ] 1 15 HHCo.

16 CH3HH jQ HHC? JHC)] 2CH, CH1
9◎ HH 2 Table 3 -=r setter 0.70 1.8
8 A 1o#0 Parking
0.29 0.50
A 6B @a
A
10Sil! 1″～ash
A 100 Hayashi
0.21 0.84
A I0 sample F 7Rp
Rg! 1 20 CH,HCNHC4Ha21
CH3Hcooc, I (522 (6〉) (cooc, H
,.

Also -1 23NHC4H9HCOOC2H5 24HHCCF3 25? JHC4) (9HCCF326
HH5O2CH3 27NHC,H,HcccJ,3 x' Dmin Dm3y
fh+f-1 everyone; shi1゜O green
A 2O8 magenta A
200 red
A 300 red purple
0.57 1). 98 A 50
1.50 1.78
A 20 Red~k O, 351
,07A 300 Finger 1.
89 2.09 A 50
Pink 0.29 0.5[]
A 15t sample R-) R
B P, g X
%51) +1)', 04 Hg
)(:lCC Tako f2 0
Bi/Ri 3i CH, HCH2CF30 Blue 32 @cH, Ca13CI13S West~W1) 35℃ (275”R) Dmin Dmax ”* Hourly opening 0.54 1.2OA 2[10,65
[], 64 p 25o, 4
o O, 48A, 200.18 [
1), 57B 3++0.53 2.1
9 A 80 The purpose and effects of the present invention will be further explained with reference to the following examples, but the specific materials and amounts cited in the examples, as well as other nesting details and other details, refer to the present invention. It should not be construed as unnecessarily limiting "1u1".

The dye used in the Examples is a synthetic leukodiazi/A dye having a subfertility structure.

CT Staph 7 Op>i og was dissolved in 250 mK of water under nitrogen. Sufficient sodium dithionite was added in the housing to be completely colorless.

Methylene chloride 200M was added and the solution was stirred vigorously with a mechanical stirrer. Benzoyl chloride 89 was added and stirring was maintained for 3 hours while adjusting the IOK of the aqueous phase. At that point the methylene chloride phase was separated, washed with water, diluted with potassium carbonate solution and washed again with water. The solution was dried over Mg5O, and the solvent was removed under vacuum to obtain the crude product. This material was recrystallized from acetate to give the product Leukodiazine A.

Example 1 A 0 icooxazine dye, par Script Turquoise 5-2G, was used in a silver soap system in the absence of metal halides with a Lewis acid as a development accelerator to produce 7
Otothermographic imaging was tested.

A Silver behenate fursozo 8. OyB
Butpal 876 0.1gC Ethanol 17.99 FD Toluene
37.89 F is - lumi time
23:04 - Down loading E Toluene 36.025' mill time 1 hour The above solution is 12
．． Milled in a 240M glass jar half-filled with 7mm glass beads.

Final silver soap coating solution 1B Mix the following ingredients and apply 0.10% on baryta coated paper.
It was coated at 16 mm (4 mil) and air dried.

A Silver saw 1 dispersion iA 69.69B
Toluene 98ml 1C Ethanol 15mJD Butpal 7376 15 9E Fluorochemical surfactant 0.29 (FC431, 3M
) Topcoat formulations The following solutions were prepared to evaluate several acids or development modifiers.

A Par is Script Turk Ois 5-20 0.
6259B Cyanrupu TJV 541) TM (U
V-absorbent, American cyanamide backing')
0.125IC ethanol/'
12.50m/D 10% by weight Gutobal B76 (
in acetone)50. Effect of OFNickel Nitrate A solution obtained by dissolving 0.19 nickel nitrate in 5 M of methanol and 5 M of N-methylpyrrolidone.
To master solution IC (no acid) 59 of this example, turmeric, m-nitrobene, and aromatic acid (master solution 1C12, 1 g) were added.
This example master solution 1 containing 0.075 g per
)c! Added to M. Use these coating solutions for silver soap coating 1B.
It was coated on top to a thickness of 0.1016 mm and air-dried. The results are shown in Table 3.

Table 3 1, No acid 10 20 0.120
．． 3230 10 0.1) 0.45 2, m-nitrobenzoic acid 90 10 0.12
0. <5230 1.5 0.420.76 The data in Table 3 shows that nickel nitrate acts as a development catalyst without the use of additional carboxylic acid catalyst.

Example 2 Silver Soap Solution 2A A halide sensitized silver soap solution was prepared using the Example 2A silver soap solution as follows:A silver y--fe
b Cloth H1B60 1) B Zinc chloride (4,32g/1
00goethanol) solution
0.1-0.076 on a 0-0508+r+m (2 mil) thick oxidized polyester film
It was applied to a thickness of 2 mm and air-dried.

Topcoat Master Solution 2B A topcoat master solution was prepared as follows: Loading Materials
Amount A 15 wt'N% Butopal B-76 (in acetone > ioo gB ethanol)
127 Ql:C Cyan Lube UV541
) 0.29 Then, 125g of Parr Script Turkoice 32GO was added to the topcoat master solution 2B109. Add a development modifier,
The obtained solution was coated with silver soap coating 2AJ:KO1)5241
Coated with TIITl (6 mil) and air dried. The resulting coating was then exposed to ultraviolet light and heated to 124°C.
It was developed with The results are shown in Table 4.

Table 4 1 0.05 talic acid 40 20 0.25
0.16 Green 20°05g'-=Fo40 2 0.
251-52 J & Phthalic Acid In the same procedure, Parr conducted an experiment using Cobichem ■ or Leucodiazine A in place of Script Turquois 82G. The results are shown in Table 5.

Layering 1) -1 ≧ 1 - ~ ~ The data in Tables 4 and 5 are... with oxason, thiazi/, or diazi/leuco dyes in photothermographic systems containing silver loronide. The effectiveness of various acids as development accelerators used is demonstrated.

Fruit Example 6 Silver Behenate Solemix 6A Silver Behenate I・-Fun-7''' 300g ethanol 2
696m! : ) Luene 347 Creates a dispersion by dispersing in Ti1l by rapid mixing. Then, this dispersion was mixed with urinmodyl 15
M 8 TBA, sND homogenized (ma/t/-
550 klF/cm2 (8000 ps)
t ) and 225kli'/cm2 (4000pst)
It was homogenized by passing it twice. Then this material 389.
89 was diluted with 6 ml of ethanol (1). Polyvinyl butyral polymer (Butvalu 876) 34.7 g
This premix was completed by mixing in a 1 hour medium.

Parr evaluated the effect of acid on the oxidative reaction between Script Turquoise and silver behenate - Fusode. The formulation was used.

A, Silver behenate solemix 3 A
50.0'9B, ethanol
6.0dC0 calcium bromide (5,729/100d ethanol) solution
Q, 41L/! D.
Acid (see Table 6) (59/1001d acetate/) solution
5. (3rnlE, Bell Script Turquoise 52G (109/1001+1/toluene) solution
3. Q, *J These coating liquids are 0.0
0.10161ff1) was applied onto a 508 mm thick polyester containing titanium oxide (3M), air-dried for 3 minutes, and further dried at 82°C (180'P) for 3 minutes. Then "BioLite" (Allied Lin Supply, Inc., CA/Francisco) via continuous stage tablets
It was exposed to an ultraviolet light source (General Electric 15W black light) for 120 seconds. Then, 3M model 70
Hot grand butt! The samples were treated with a σ setter at 127° C. (260 F.) for 1 to 120 seconds, and the density was measured with a Macbeth densitometer using a red filter. The acids tested are listed in Table 6 below.

Table 6 1.7 Talic acid 75 0,22 1
．． 32 Green 2,4-nitrophthalic acid 1
0.52 1.36 Blue 4-nitrophthalic acid was re-evaluated in conjunction with a 0.4-solution of mercuric chloride (0.57 F/ioomg ethanol) and 59 ionox for the test solution formulation. The same process was repeated with the addition of 3.0 d of TM(R) 201 antioxidant (Shell Chemical Company). These coating solutions were applied and tested in the same manner as in the previous example. The results are listed in Table 7.

Table 7, Control 1 0,521.36 Blue 2, Combination with mercuric chloride 2 0.18 1.4
4 The data in Table 7 for the front cylinder show that mercuric chloride, with or without an antioxidant, can be used as a Lewis acid type development accelerator and as an antifoggant in the present invention.

The effects of various acids on the redox reaction between Cobichem ■ and silver behenate half soap coated with Cobichem ■ and acid were evaluated. The following formulation was used for this evaluation: Ingredients
Amount A, Behe/Acid Silver Premix 3A
30. [l 9B, ethanol 3. Q
m1C0 Calcium chloride (5,72F/100d ethanol 0.4 1nl) solution, acid 0
．． 15FE, Acet/3.0 GoF, Copichem [r (5 g/100 mA! Toluev) solution 6.0 d These coatings were applied, dried and processed as described in Example 3B. Acids are listed in Table 8.

Table 8 1.7 Talic acid 90 0.19 0.2
7 Yellow 2,4-nitrophthalic acid 20 0,6
4 0.97 Blue 6.4-chlorophthalic acid 55
0.22 0.48 Oxidation of behenic acid pot-coated leucodiazine A containing green leucodiazine A, acid and toning agent and silver behenate half soap -
The effect of acid on the reduction reaction was evaluated. The following formulation was used in this evaluation.

A, Silver behenate solemix 3 A
30.09B, ethanol
4. QmlC0 mercuric chloride (0,579/1
00L/ethanol) solution
C1,4mD, calcium chloride (5,7
'J/10 Dgoethanol) solution
0.4dE, acid (5g/10
0m) Solution 3.0pF, Oikodiazi-/A C6! i'/100rn1 acetone+
i, 2r! 3.0 ml of LtNMP (N-methylpyrrolidone) solution These coatings were applied as described in 6B, dried and processed. The materials evaluated are listed in Table 9. Measurements were performed using a green filter.

Table 9 1. Phthalic acid 150.161°28
Magenta 2・7'u""+10 0.15 1.
38 ~yyp Phthalic acid 4 [1.5 mJ of phthalazinone (2,5zo/100 m methanol) solution was used] The data in Table 9 shows that the combination of phthalazine/7thalic acid has a higher image density than phthalic acid alone. It shows that it gives.

Example 4: Evaluation of metal nitrate salts when used with leucooxazine dyes Silver behenate premix 4A Dye-sensitized /% silver chloride-containing behenate/silver acid half-hoop system containing oxazi/and thiazo A silver behenate premix was prepared for use in evaluating the use of metal nitrate salts with /leuco dyes. Silver behenate homogenate 4A was used.

A, silver behenate homogenate 4 A
389.89B, N-methylpyrrolidone (NMP)
2.4GoC,TohWork:y

6.01nlD, ethanol
1[]4.07+1JE, Butpal B
76 (0,59/100ml: r-tanol) solution
Q, 9 m
IF, Butpal B 76
3/1.6 So sensitized silver behenate premix 4B and 4 solution premix 4A were halodanized and dye sensitized to green light with the following formulations:
Amount A, silver behenate premix 4A 50
g50 FB, ethanol
20 go 20 ru.

C, mercuric bromide (0,579/10 QmJztanol) solution o o, ymt
D, Calcium bromide (5,725'/100 ethanol) solution 0.7d 0.7R
/E, RP421 dye (0,19/1D 0ml ethanol) solution 1.3m 1.
3 m This coating solution was applied to a thickness of 0.0508 mm on a 0.0508 mm thick polyester containing titanium oxide (6M).
It was then dried at 77°C (170"Fi') for 3 minutes.

This was done to evaluate metal nitrates used in top coats containing polymers with leuco dyes and 7-talic acid.
used.

Topcoat Master Solution 4D A topcoat master solution containing parr script turquoise for Lewis acid (nitrate) evaluation was prepared using the following ingredients: A. 10% by weight CAB-553-0-4 (in ethanol) ) (Alcohol-soluble cellulose acetate butyrate manufactured by Eastmano) 120.
0 gB, phthalic acid
0.6yC1+Par Script Turkoice 82G 1.2 9D, N-methylpyrrolidone 12.234g This leuco dye was pre-dissolved in N-methylpyrrolidone before mixing with the polymer solution.

The nitrate was previously dissolved in methanol at a concentration of 1 part per 100 d. 2.34X 10-
Added to topcoat master solution 4D to give an equivalent concentration of 5 molar metal nitrate. .

The evaluated nitrates and their usage amounts (9) are shown in Table 10.

Nickel nitrate 6.8 Aluminum nitrate 8.8 Ammonium nitrate
1.9 These topcoat solutions were applied to the top surface of silver behenate coatings 4B and 4C, respectively, with an orifice setting of 0.1016 mm and 77°C (170°F).
') for 5 minutes. They were exposed to a xenon flash (EG&G SE/Sitometer) for 10-3 seconds via a continuous tone wedge and then heated to 124°C (255'F') in a 3M Mauser 70 heated blanket processor.
The film was developed by heating for 20 seconds. The resulting wedge was measured with a computerized densitometer using a red filter. The results are shown in Tables 1) and 12.

1 None, 06 0.60 216 7
822 Nickel nitrate, 1) 1.53 16
2506 Aluminum nitrate, 1. ! 5 1
．． 44 27° 1404 Ammonium nitrate
, 08 1.22 31° 174 Table 12 (
Behe/acid silver sol mix 4 (no 15, 0
7 1.40 40° 8766 Nickel nitrate
,06 2.1657° 4497 Aluminum nitrate ,09 2.04 53° 2528
Ammonium nitrate, 07 2.1655° 65
The data in Table 9 (1) show that Lewis acids (nitrates) improve the thermal reactivity of the system, giving higher image density, r-angle, and photosensitivity. The color of the image of the above system was blue to sheer.

Example 5: Evaluation of nickel nitrate and nickel bromide as development accelerators when used with leucothiazine dyes Sensitized silver behenoate premix 5A Solution premix 4A' prepared in Example 4 was prepared with the following formulation: Halogenated and dye-sensitized to green light.

B, mercuric bromide <0.579/100 goethanol)
Solution 2.8d
C0 Calcium Bromide (5,721/100ml x Tanol) Solution 2.81
nlD, mercuric acetate (1,729728 mJ methanol) solution/I!
2.8pE, #421 dye < o, i o'i/1o
ogoethanol) solution
5.2 ml of this coating solution was coated at 0.0508 mm onto a 0-508 mm thick polyester containing titanium oxide and dried at 77'C (170'F) for 6 minutes.

Topcoat Master Solution 5B A topcoat master solution containing Copichem ■ for metal nitrate evaluation was prepared with the following formulation: Ingredients Amount A, 10% by weight CAB-553-0-4 (in ethanol) 160.0p
8.4-Nitrophthalic acid
0.8yC, Copichem U
1.6 pD, N-methylpyrrolidone 16.43 F [(A)
Nickel nitrate evaluation Nickel nitrate and phthalic acid were separately dissolved in ethanol at 19 degrees per oomt.

Then add 0.5 ml of each of these solutions to 22.354 ml of Top Coat Master Solution 5B! i' was added. Sensitized silver behenate coatings 5A, f:
at an orifice setting of O-1016trrn and dried for 5 minutes at 77°C (170''F).
etc. were exposed, processed and tested as in Example 4. The results are shown in Table 13: No. 16
Table 1 Phthalic acid 90 0,140.93 25
3.8182 Nickel nitrate 90 0.1
6 1.35 44 1.000 This data represents the effectiveness of nitrates as development accelerators.

Example 6: Combination of other leuco dyes with leucooxadi/and thiacin dyes Topcoat Master Solution 6A To evaluate the effectiveness of the combination of oxazino and thiazo/leuco dyes with nickel nitrate, 4-nitrophthalic acid and leuco A top coat master solution containing crystal violet was prepared. The following formulations were administered: A, 10% by weight cAg-553-0-4 (>200.0 in ethanol)
F8.4-ditrophthalic acid
1.09C, Leuco Crystal Violet (manufactured by Aldrich Chemical Company)
0.2 g of Script Turquoise, Cobichem ■, and nickel nitrate were pre-dissolved in the solvent and then 20.12 g of Example Top Coat Master Solution 4
Added to G. The following solutions were prepared: Volume A, Master Solution 6k 20.125' 20
．． 12! i' 20.12g20.12! i'D, 1.
05' Nickel nitrate/100m methanol 0 0. 5d 0.5
1) 14' CJ, 5mi These coating solutions were applied to 0.0762 m of silver behenate coating 5A, and heated to 77°C.
(170°F) for 5 minutes. They were exposed, processed and tested as in Example 4. The results are shown in Table 14.

All images are bluish green. Q9- of Table 14
The results show that the leuco dyes of the present invention provide effective systems in combination with other leuco dyes and nickel nitrate.

Example 7 The following formulations 7A and 7B were used to evaluate the effectiveness of phthalazine: Amount B, 1.2 tapars of script Turkois 82G/12MN-3,0m 3.0
mMethylpyrrolid/C, phthalic acid 0.309
0.30! ? D, 4-nitrophthalic acid
0.01 0.05gE, Tetrachlorophthalic acid 0.035' 0.0351F
, Futaraj 10 O, 0351 These solutions were applied to a skin thickness of 1016 m on silver behenate thread fi4c and heated to 77°C (170°C). ) for 5 minutes.

They were exposed, treated and tested as in Example 4.

The results are shown in Table 15.

7A control 15 0,1) 2.1358° 1667
B Use of phthalazine 60 0.08 1.68 3
8° 1422 These samples are 2152 mm)
(2000 foot candles) aged for 2 hours at 27°C (80°F') and 60% relative humidity. L'llll l
Table 15 shows the changes in n.

7A O, 130, 95 doo 0.807'B O
, 120,49+0.37 The data in Tables 15 and 14 show that conventional developer modifiers used in dry silver are also effective in this system. Phthalazine reduces thermal reactivity but improves silicate stability.

The combination of phthalazine with nickel nitrate and pars script turquoise was evaluated in the following formulations.

Amount B, phthalic acid 0.09i
0.093so C,4-nitrophthalic acid
0.028g methanoltanol These solutions were coated at 0.1016m onto Behe/Acid Silver Coating 4c and dried at 77°C (170'F') for 5 minutes. They were exposed, processed and tested as in Example 4D. The results are shown in Table 17.

The data in Table 17 contains nickel nitrate/futafuji/
demonstrated increased concentration and sensitivity of the construct. 7 When compared to Talazine alone, the addition of nickel nitrate improved sensitometry without harming print stability.

Example 8: Acid and oxadi/dye cyan silver coating solution 8A (below) was prepared and coated with a 0.076 mm thick VoIJ ester film "Melinex Format" Type 329 (ICI) in a laboratory manual knife coater.
The coating was applied at 3.6'i/m2 (0.32, S'/sq. ft.). Various acids were used to construct the leucooxazine dye par with script turquois s2c.

Cyan silver coating liquid 8A 8 Cyan silver coating liquid 3B (Example 3)
90 FB ethanol
36 ccCO, 365'mercuric bromide/
10 (IIIX: Methanol 2ccD 4.0!?
Calcium bromide/100cc methanol 1.8cr.

150CC Methanol 0.064 mm (2,5 mil) Orifice: 82°
Dry at C (18[+'l?) for 5 minutes.

One coat of the following formulation was used to evaluate acid in the top coat over a previously applied red sensitive silver coating (8A).

Cyan top coat solution 8B Aidu amount% CAB-553-025! i'B Test acid 0.6 or 0.4 sol surfactant top coat applied with 0.076 mm Oryswiss.

Dry at 82'C (180'F) for 5 minutes. after that.

The material was exposed to an Ell & G xenon flash sensitometer for 10-3 seconds. No filter was used. The samples were processed in a 5M Model 70 thermal cylinder 7-ket processor at 124°C (255°F'). Table 20 shows the residence time, Dmin-Dmax, with the test acid.
is shown・1, benzoic acid 0.3 60
0.08 0.102, salicylic acid 0.4
20 0.45 1.756.6-chlorobenzoic acid 0.4 60 0.27 0,39
4.2-chloro o-4-2) 0.4 10
0.35 2.360 Benzoic R200,733,05 5,2,4-dichloroben 0.4 10
0.17 1.67 Zozoic acid
20 0.23 2.08 ■, aromatic acid/acid 1.7 talic acid 0.3 20 0
．． 08 2.002, homophthalic acid 0.
4 60 0. -08 0.9836 Phthalic anhydride 0.4 20 0.08 2.03
4.4-Methylphthalic acid 0.4 20 0-
09 2.475.4-Ditrophthalic acid 0.4
20 0.10 1.766.3-nitrophthalic acid 0.4 60 0.08 0.637, tetrachlorophthalic acid 0.4 20 0.1)
0.519, Sarakari 10.4 60 0.1
0 0.55■, aliphatic dicarboxylic acid 1, maleic acid 0.4 20 0
．． 18 2.2 filter 2, itaconic acid 0
．． 3 60 0.08 0.763, gel taco/acid 0.4 60 0.10 CL4
34, dichloromaleic acid 0.4 20
0.10 2.655, malic acid
0.3 60 0-10 0-986, tartaric acid 0.3 60 0.08 0
．． 481, citric acid 0.4 60
0.09 1.04V, nitrate 2, ammonium nitrate 0.006 600.200
．． 45-Pore Polycyclic Aromatic Cicarpic Acid The data in Table 20 demonstrate the effectiveness of various acids as development accelerators for use with PargaScuri 7' Turquoise 82G in color constructions.

Example 9 A dispersion of silver behenate half-sozo was prepared at 10% by weight in a mixed solvent of toluene/90% and ethanol 10%, and the m/ton was 550 kg in a urin homogenized model 15M.
/225ksT/cm for river 2 (80004oo.

psi and Vto-Jpsl> twice. This silver soap dispersion is then diluted with the solvent at a selected time and mixing sequence.

It was prepared for coating by adding a halodephide, a polymer, and a sensitizing dye.

Magenta silver coating liquid 9A B Tolue: y
1755'ac
0.1. F75HE
5cc95IP 3c
c100JC78!9220 Stop mixing at 340 minutes. 905' in Example 1 is n,
013 @ dye 150CC methanol concentration #534
Dye sensitization was carried out using a 2.7 mm dye (green sensitizer) solution. This solution was applied to a laboratory manual knife coating machine at 0.076rrtm.
(3 mil) 0.05mm (2 mil) by orifice
It was coated on top of a thick polyester film containing nathane dioxide (3M). This @ membrane is 5 at 81℃ (177'F)
Dry for a minute.

Magenta Top Coat 9B The following top coat solution was prepared for coating on the top surface of Magenta Silver Paint 9A.

Loading material
Amount A Toluene 34 CC B Ethanol 1
0 CCC phthalazinone
0.16@D Tetrabromophthalic anhydride
0.16-9G magenta leukoi/ls7 niline dye 2,6-dichlorophenol 8.159 in 600M water
and 15.9 F of sodium carbonate were dissolved: then 150 rL of chloroform was added. Potassium felicium oxide in 60°d of water 65.9! Add a solution of i+,
The solution was then stirred for 1 hour. The chloroform phase was separated, washed with 5% aqueous sodium hydroxide, dried over Mg5O4, and stripped to yield the dye. Add this dye 19 to 2 ethyl ether 2001) Ll! and 0.58 F of t-butylhydroquinone was added.

This mixture was left for 6 hours. The mixture was extracted with an aqueous solution of ether (5% hydroxide). The aqueous phase was separated and acidified with 10% hydrochloric acid. A precipitate formed. This suspension was extracted with ether.

Evaporation of the ether gave a pale brown material magentaloid aniline dye.

This coating solution was applied to the top surface of 1) 1E9A using a 0.076 rnm (3 mil) orifice, and
7″F) for 5 minutes.

Another dispersion of silver behenate halfunzo was prepared in the same manner as 9A except that a mixed solvent of 90% ethanol and 10% toluene was used. This silver soap dispersion was used to prepare a red-sensitive coating solution for a cyan color system to be coated on top of a previously applied magenta color system.

B Ethanol
104Ql: C Butopal B76
1F cyan silver coating liquid 9D Loading material
To quantity cyan silver premix 90
90 gB ethanol
36 MSD 563 dye (red sensitizer) dissolved in 50 g of Ql Nidia Ampere Mix 9C solution in methanol with a concentration of 0.017 x 15 Qcc i1.2c
Dye sensitized at c. This was applied through a 0.05 mm (2 mil) orifice on top of the previously applied layers 9A and 9B. The coating was dried at 81'C (177°F) for 5 minutes.

Cyan Color Topcoat 9D The following topcoat solution was prepared for coating on top of cyan silver premix 9C to complete the magenta/cyan color pie pack.

Loading material
Amount A ethanol
40 al:B Phthalic acid
0.50? C4-Nitro7talic acid 0.2. H'D 1
5fold i='oCAB-553-0/in ethanol
68 9F Toruev
10C was applied to the top of the cyan silver premix 9C through a 4 mil orifice and dried for 5 minutes at 177F. A maze/li/sheer/vipack was thus completed, which had the following structure: base o, osmm thick (2 mil) TlO2-filled polyester first layer - green sensitive silver second layer - barrier weight. Magenta color developer and development modifier in the 3rd layer - Red-sensitive silver 4th layer - Cyan color developer and development modifier in the hard Tozzo coat polymer This material produces a magenta/magenta color and a cyan color. EG&()(EG&
G Company Electro-Optics Division, hta, J ((Salem)) exposed to xenon flash sensitometer.
did. Latuten/PIIL58 and Latuten 525 were used. The exposed material was then heated to 124°C (255F).
) for 20 seconds.

The sensitometry of this pie pack is shown in No. 18.

Dmax O, 260,
23Dmin 1.57
2.20γ angle 54
65orgs 7cm2 (0.6 degrees/fogging)
64 21 Image color
Magenta Cyan The data in Table 18 shows that good color separation was achieved and demonstrates the utility of the two-color system.

Example 10 Next, the cyanoxadi/leuco dye par was
A six-color separation system using turquoise will be exemplified.

Yellow silver coating solution 10A This solution has a concentration of 0.032 g. Dissolve #454 dye (blue sensitizer) in 150 cc methanol.
It was prepared by adding silver paint 9A40F.

This was coated onto a 0.0508 mm thick (2 mil) polyester film with titanium dioxide (3M) using a laboratory manual knife coater with a 0-1016 rrrm (4 mil) orifice. The coat was dried at 81°C (177'F) for 5 minutes.

Yellow top coat Itsuki 1 effect premix IOB loading
Materials Amount Charges B and C were mixed: τ before being added to Charge A.

A Methanol 12
CCC phthalic acid
0.04 9D 4-methylphthalic acid
0.08 ZoE Tetrachlorophthalic acid 0.05 9F Phthalazine 0.12
5'7G Resin premix 10B
40 g Charge Materials B-F were pre-dissolved in Charge Material A prior to the addition of Charge Material q. This solution was applied to the top surface of the previously applied yellow silver [9A, 0.07
6 (3 mil) orifice and heated to 79°C (1
75'F' for 5 minutes.

Magenta color systems 9A and 9 described in Example 8
B was applied on the upper surface of the yellow coloring system. The resultant was exposed and processed according to the procedure of Leprosy Example 9. For yellow color, Latte/Ryo 47B (blue light) was used.

The sensitometry of this yellow/magenta pie pack is shown in Table 19.

'may O, 300, 31
”min 1.79 1
．． 50γ angle 50° 5
3゜-4r gs/crr? (at 0.6 density/power free) 2725 Image Color Yellow A cyan coloring system utilizing magenta cyan silver premix 9C and shea/silver coating t9D was applied to the top surface of the yellow/magenta pie pack. Yellow, magenta, and sheer sensitometry was obtained in the same manner as described above. The results showed good six-color separation suitable for color reproduction. The yellow sensitometry was the same as the pie pack, and the magenta and cyan were the same as disclosed in the maze/li/cyan pie pack.

Various modifications and variations will become apparent to those skilled in the art without departing from the scope and spirit of the invention. The invention is not unnecessarily limited to the exemplary embodiments described herein.

Claims (9)

[Claims] (1) A photosensitive and non-photosensitive silver source, a binder, an oxidizable leucofenazine or phenoxazine or phenothiazine dye as a reducing agent for the silver source, and a carboxylic acid or Lewis acid or Bränsted as a development accelerator. A single sheet negative-acting photothermographic construction having on a supporting base at least one photosensitive chromogenic element consisting of an acid, wherein the color of the image is provided by the oxidized form of the leuco dye. (2) The composition of claim 1, wherein the photosensitive silver source is silver halide. (3) a) The leuco dye has the formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, each R may be the same or different, and individually represents i) halogen, ii) unsubstituted aryl or an alkyl group, or such a group substituted with up to four groups selected from alkyl, alkoxy, cyano, hydroxy, halogen, alkylsulfonyl, arylsulfonyl, and Z, where Z is as defined below. , provided that both alkyl and alkoxy groups have 1 to 20 carbon atoms,
and iii) Z (however, Z includes ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and each Q may be the same or different, and individually i) halogen ii) unsubstituted Aryl or alkyl groups, or those substituted with up to 4 groups selected from alkyl, alkoxy, cyano, hydroxy, halogen, alkylsulfonyl, arylsulfonyl, and Z, where Z is as defined above. R′ may be the same or different and individually represent hydrogen, halogen, selected from alkyl or alkoxy of 1 to 6 carbon atoms, or the like substituted with up to 3 halogen atoms; X is -S-, -O-, or -NQ-; L is hydrogen or Z; with the proviso that R and L together can have up to 5 carbonyl and sulfonyl groups; Formula R^1^0(COOH)_n (wherein n is an integer with a value of 1 to 4, and R^1^0 is unsubstituted or amino, hydroxyl, aryl, lower alkyl, lower alkoxy, cyano , sulfonyl, mercapto, nitro, halogen atom, and Z (where Z is as defined above): However, when n is 1, R^1^ 0 is selected from the group consisting of alkyl, alkenyl, aryl, and phenylalkyl of up to 10 carbon atoms, and when n is 2, 3, or 4 R^1^0 is up to 14 carbon atoms, ii) halides, nitrates, sulfates, sulfonates;
and iii) at least one acid selected from brensted acids selected from sulfonic acids, sulfinic acids, phenols, phosphonic acids, phosphinic acids, and sulfimides, and the color of the image The composition according to claim 1 or 2, wherein is provided by a phosphide of said leuco dye. (4) The leuco dye has ▲mathematical formula, chemical formula, table, etc.▼, ▲mathematical formula, chemical formula,
The composition according to any one of claims 1 to 3, which is ▼ ▲ has a mathematical formula, chemical formula, table, etc. ▼ or ▲ has a mathematical formula, chemical formula, table, etc. ▼. (5) The composition according to any one of claims 1 to 4, wherein the carboxylic acid is substituted benzoic acid or naphthoic acid. (6) The composition of any one of claims 1 to 5, wherein the Lewis acid is selected from nitrates of Ni, Zn, Al, Cu, Hg, and NH_4^+. (7) The composition according to any one of claims 1 to 6, wherein the color-forming element has a single layer structure. (8) The composition according to any one of claims 1 to 7, wherein the coloring element has a two-layer structure. (9) The structure according to any one of claims 1 to 8, which is part of a two-color or three-color separation recording system.