JPS5948765A - Formation of color image by heat development and diffusion transfer - Google Patents

Abstract

PURPOSE:To form a color image with superior stability, etc. by imagewise exposing a heat developable photosensitive material contg. a specified dye providing substance, developing it by heating to form an imagewise distribution of a chelatable sublimable dye, and transferring the dye to an image receiving layer contg. multivalent metallic ion by heating. CONSTITUTION:A heat developable photosensitive material is obtd. by coating a support with a layer contg. a binder such as gelatin, photosensitive silver halide, the silver salt of an org. compound such as silver behenate, a developer such as the compound represented by formula I , and a heat nondiffusible dye providing substance capable of releasing a chelatable sublimable dye as a function of development, e.g., the compound represented by formula II or III. The photosensitive material is imagewise exposed and developed by heating to form an imagewise distribution of a chelatable sublimable dye from the dye providing substance. The dye is transferred to an image receiving layer contg. multivalent metallic ion such as copper ion by heating to form an imagewise distribution of the sublimable dye chelated with the metallic ion in the image receiving layer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to heat-developable color diffusion transfer image formation, and more specifically, the present invention relates to heat-developable color diffusion transfer image formation. The present invention relates to a developed color diffusion transfer image forming method.

Color image forming methods using a photosensitive substance (silver halide) include, for example, a method that uses a dye formed by an oxidized form of a coloring agent and a coupler, and a method that uses silver to bleach the dye to obtain an image. (silver dye bleaching method), or the color diffusion transfer method, in which dyes used in so-called instant photography are diffused and transferred using an alkaline solution, but these methods require a water bath treatment af. However, it has the drawback that the processing required to form the image is complicated. Therefore, there is a strong demand for the development of a photothermographic color image forming method that can form color images using a dry process and simple processing.

As a method for forming a heat-developable color image IW, for example,
No. 4-7782, U.S. Patent No. 3,761,200, U.S. Pat.
No. 7132, and rTj156-27133. Is there a method for forming a single color image using an oxidized form of mulberry and a coupler as a color developer? In these methods, a silver image is also formed where a dye image is formed.
Color turbidity/staining occurs due to the silver image, and staining of the white background occurs due to the printout after discipline. To eliminate these problems, desilvering, fixing, and heat-developed photography are essential.
The advantage of the note method is that it has a processing power that is easy to remove.

Other thermal development color image forming methods include, for example, JP-A-52-105+421, JP-A-52-105822,
No. 56-50328, US % Total No. 4,235,957
There is the Tsuru dye bleaching method described in the issue.

However, the method of R7 et al. requires the use of an activation sheet containing a strong acid or a halogenated initiator in order to bleach the dye image, making the process complicated and using strong ribs. It has the following disadvantages.

Yet another A'! For example, as a method for producing actual color printing, there is the colored yarn wholesale method described in Research Disclosure 16966 published in May 1978.

This method is a way to compensate for the shortcomings of the above two methods.
However, it is difficult to fully understand the process of synthesizing the dye, tR, and because the dye becomes a silver salt and the dye is IA and Z, it is difficult to understand the image. This results in fog. Furthermore, the pigment is dissolved at 21:00 by turning the base plate at 21:00. It has the disadvantages of 1. ．． “V exists.

One object of the present invention is to provide a method for forming a thermal color diffusion transfer image using a sublimable colorant having a chelating compound and a sublimable dye-donor. .

A second object of the present invention is to provide a method for forming a heat-developable color diffusion transfer image in which the formed 1-size multicolor image is stable against spinning, light, humidity, etc.

Purpose of the above research LL, thermal development color diffusion transfer + [! I
In the i-image forming method, a gylatable #P sublimable dye is released as a function of development, and after imagewise exposure of a heat-developable γL material containing a thermally non-diffusible color-providing substance, By developing, an imagewise distribution of a sublimable dye that can be chelated is formed from the color-providing substance, and at least a part of the imagewise distribution is formed with polyvalent metal ions that are also in a stacking relationship with the thermal elongation light-sensitive material. This was achieved by thermally transferring the phosphorescent dye to an image-receiving layer containing polyvalent metal ions to form an imagewise distribution of the phosphorescent dye chelated with polyvalent metal ions in the image-receiving layer.

``Sublimability'' generally refers to ``the property of changing from a solid to a gas through several body states,'' and there are many dyes that exhibit this sublimability in the industry. (Specific examples (shown in Dye Handbook-1 (round neck)) Sublimable dyes are non-transparent solids at 1 temperature, and in the presence of a bath medium, r ), it is non-diffusive.When it is heated and exceeds a certain temperature, it sublimates and becomes a gas.
It shows diffusivity and moves through space. II'-J- is possible. For example, a sublimable dye t-↓ coated on a support
, vaporizes by being heated and diffuses away from the support 1. attitude<. Also 1. If there is an image-receiving layer nearby, even if it is not in close contact with the support, it will adsorb and precipitate inside the image-receiving layer to form a dye image. It also has the ability to diffuse and move between layers,
ing. That is, even if there is an intermediate layer between 1- from which the sublimable dye is released and the image-receiving layer, the bath! It is a wonderful thing that requires one's body (diffuse 1 to 2] to do 7) - something that can be done. Therefore, by utilizing this characteristic, it is possible to
(1-It is also easy to set up a color heat-developable optical material 4-i.

The dye image formed does not have the drawback of using a sublimable dye - re-sublimation - when it is chelated and has a non-sublimable system. First, according to Akira's method, an image is generated and fixed using only heat processing, and a color image can be obtained with extremely complicated processing.

Of course, since the present invention uses a diffusion transfer method, desiliconization is not necessarily required, and since the image formed is a chelated dye image, it is stable against heat, light, moisture, etc., and is particularly resistant to YF and durability. Right away
This is a dye image.

In this research, the sublimation temperature of the sublimable dye that can be converted to 1.5% is 50-2".
℃, and is a dye capable of forming a complex with a polyvalent metal ion with a distribution of at least 2 Pl or more, and is more preferably 1. <Sublimation temperature>j; 50-170℃
It is an azo dye that can form a tridentate gyrate complex.

Compared to the conventional, so-called instant photography method, in which the dye forms an image by diffusing it in a concentrated alkaline solution that is harmful to the human body, the color thermal diffusion transfer force method of the present invention transfers the image by simply heating it at a fixed temperature for a fixed period of time. It is safe and excellent in that it does not allow images to be obtained.

Also, in the conventional method of copying the seven dyes formed or released in the thermal image-sensitive material by thermal melting ('v-malsolvent), , the multi-relayer force equation is difficult.

In the present invention, the color-providing material is thermally non-diffusive and does not actually cause intra-layer or inter-layer diffusion even when heated. In the present invention, the color donor 'h is 1↓ of development.
It is a substance that can release sublimable dyes or sublimable dyes and cursors, and can be released directly through the redox reaction that occurs during development, or via the intermediary of cross-oxidizing agents, etc.
A release reaction occurs by direct action.

Reactions in which a color donor releases a sublimable dye Mamekol↓ sublimable hydrogen cursor include decomposition, elimination, ligand'/j: conversion fc, -, etc. In the present invention, , the diazo coupling method or the oxidation coupling method is effective when using a coupler with an occupancy point of 16' and a thickness of J of 7.

For example, an oxidized form of an aromatic-grade amine color developing agent can be formed by diazo coupling or C oxidative coupling between an oxidized product of an aromatic-grade amine color developing agent and a coupler having a ballast base at 2 through a bond at two points. This is due to the fact that the dye has sublimation properties. - For example, a liquefied product of a aromatic group-grade amine color development agent and the active site is sublimated: dye or sublimation property 9. Diazo coupling or oxidation coupling with a coupler having a precursor as a leaving group is a reaction in which the lunar color precursor is released.

The method of the present invention comprises a non-diffusible color-donor material (hereinafter simply referred to as [color-donor material]) capable of releasing the chelated color pigment according to the present invention. Set to 1.

) include compounds represented by general formula (1).

In the formula, E.sub.lk7 substituents include an alkyl group, an alkoxy group, a cyan group, a hydroxyl group, a thiol group, a thioalkoxy group, or a halogen atom.

X2 is the same as that defined in general formula (1), and may be substituted with an appropriate substituent on the ring, and preferable rings include rrbenzene+, 1, naphthalene salt, pyridine ring, or gynoline ring. and preferably (-) the substituent □ is an alkyl group, an alkoxy group, a cyano group, a hydroxyl group, an amino group or a halogen atom. group, thiol group or thimealkoxy, JA'Jte.

A has the same meaning as defined in general formula (1).

Another Koto 1. As a matter of fact, the general formula (2) is
There is something special about the expression ti-ru.

General formula (2) In the formula, Xl and A (the dimensions are the same as those defined in the fl-injection formula (1). Lz < it is an acetyl group, a benzoyl group, an /ano group or a [attotomido group], Z2 is an alkyl group (1-. - phenyl group).

General formula (1) and equation 12) In F/, the heat development function expressed as A'7' and l, and 'A decomposition 1<1 dye site /i
Qout]-2 There is a twill that can be expressed as Urujo and [te υ dimension 10゛ 已-hji formula (3) or (4)].

General formula (3) General formula (4) 7 In the formula, R+ + Rz + Rx + R< r ”*
+ "a + R7L'! HiKHVr fidgety,
Hydrogen atom, halogen atom (Kuito L <.1 earth atom, bromine atom, iodine atom), alkyl group (preferably [2〈 is an argyl group having 1 to 24 carbon atoms, for example, a methyl group , ethyl group, t-butyl group, s-octyl group, pentadenyl group, cyclohexyl group, trifluoromethyl group,
Henjiruno A, phenethyl group, etc.), aryl,! i1
．． (e.g. phenyl group, naphthyl group, tolyl group, mesityl Mfc, etc.), Anru, JA (e.g. ahythyl group,
Tetradecanoyl group, hivaloyl group, benzoyl group, etc.), alkyloxycarbonyl group (1++1, V
r methoxycarbonyl group, to:'zyloxycarbonyl group f < t), aryl linker # ho = # group (('illλ, fugonoxycarbonyl group, P'-)lyloxycarbonyl group, α- naphthoxycarbonyl group), argylsulfonyl-4 (e.g., methylsulfonyl group), arylsulfonyl group (e.g., phenylsulfonyl group), force/L//<moy/+4' (e.g. Methylcarbamoyl/L'!, butylcarbamoyl group, butrabucylcarbamoyl M, N-methyl-N-dodecylcarbamoyl group, phenylcarbamoyl group),
Anruamino group (e.g. 4-1n-butylamide group, β-
Phenoxyethylamide group, phenoxyamide group, β-
methanesulfonamidoethylamide group, β-methoxyethylamide group), alkoxy group (preferably an alkoxy group having 1 to 18 carbon atoms, such as togomethoxy group, ethoxy group, octadenyloxy group), sulfur It does not contain a moyl group (e.g., a memorsulfamoyl group, a phenylsulfamoyl group), a sulfamino group (e.g., methylsulpoamino, tolylsulfoyl), or a hydroxyl group.

However, 2, good-f I, <&;t Rlt R1+
at least one of Rs and FC4 and R5t
R6*R? and at least one of R6 contains a ballast group that reduces thermal diffusivity, for example, a group containing a hydrophilic group such as a sulfo group, a carboxy group, a hydroxy group, or an alkyl group, and has a carbon atom number of 8 It has five groups as shown above.

Also, at least one silk of R1 and R2, R3 and R4, and at least one silk of R3, R6, R, and R7 are bonded to each other, and 5 to 6 of saturated or unsaturated 'A11 are bonded to each other. It may also form a membered ring.

It is a divalent bonding group represented by ( ) (where L represents an oxygen atom or a sulfur atom), m represents O or l, and when m is 0, it is represented by the general formula (3)! The group is directly bonded to the chromatic residue: x.

The active point K of a naphthol- or IT-fer type cyan coupler based on the group represented by the above general formula (3) was obtained by using the cyan coupler for 41 nights. As such, any 2-cyan coupler known in the art can be used.

Next, 2 bottles for ¥1) 4, 2+ f”□, development h・;(
Optical materials will be explained. 8 current IN/r knee Mitsurishina, -1:i which forms a black and white image using a conventional button, and 1~, for example, the Tokko Kokko Showa 43-4! l No. 24, (i
+ 43-1 c: + No. 166, No. 46-4728, No. 44-26582, No. 45-127 o 0, No. 45-11 (416+, and JP-A-49-526)
As described in No. 264, etc., No. 11 (・2), from the support, photosensitive halogenated silver, i. Structure 1jK has been established, and even in the case of non-invention 1, the above-mentioned J) previously known 4-
Tax statue A! Four-light materials can be used.

As a heat-developable photosensitive material, a color R1 agent, a chemical sensitizer, a color R1 agent, a chemical sensitizer, a color stabilizer, an antifogging agent, a spectral sensitizer (excluding spectral sensitization), a two-ilter dye, an antihalation dye 4/F, etc. are used for development. 1. Physical properties of the above-mentioned heat-developable photosensitive material - support, which may be added;
Photosensitive haloken silicon, '4-Jan compound gold wire (silver)
Chibun 1- complex, decisive ball Aij, binder, color 1-14
Chemical J"11 Sensitizers, developing agents, antifoggants, pre-spectral sensitization, filter dyes, antihalation dyes, etc. - Research Disclosure Magazine 9 published in June 1978. 15 pages (C further review f,
<Mishi, Lysa11, TeiA. .

About the structure of the heat-developable photosensitive material 1 according to the present invention 5
1.

According to the present invention, the thermal development layer (A) is coated on the support by at least one layer (A) consisting of Al.
) (8) Photosensitive 11 halogenated button in the f1 size binder,
(b) Sexual group of Yagura compound, (c+ 'nf: * heat transferable material such as active drug, and (d) Fu411 1-1-1 斯 toshi? target, -1111: Consisting of given substance, component (al, ( bl,
(ci and (dlPJ< Jl, f'#1 can react to each other M stick? "That one ke τ each ITjl-)
It may be a layer or a separate layer, and the absorption wavelength of the color 1 and 9'η quality is
And the feeling of being chased '／'l': el+ノ・
Roken Kaden's first master is the major area and the J meter in the square:
IT color donation! i! Vl'jTketlll
So...Loken (2ㅅゑのΔ戊'U: をはにあとなないかん゛), ν) 1chi/lie example halogen station 1 Ij (Derit L? fK light power direction and Shugenkaku 11/7
"I Δ71""1 layer) i7 included A 1 sano 1/, or good I 1. stomach.

However, 115 catties are the absorption of C color 1 no ξ given substance J1\(,i:
, 9 length is different from the absorption wavelength of the chelate dye produced in the 9131 layer, and does not overlap with the photosensitive range of the photosensitive halogenated silver in combination with the absorption wavelength of the chelate dye produced in the 9131 layer. Silver can be included in the same layer.

In a preferred embodiment of the present invention, the heat-developable photosensitive material is provided on a support in yellow, magenta, and
It consists of three different layers (A) containing a color-donor material that emits a dye capable of forming a dye image, and a correspondingly spectrally sensitized silver oxide. Because the dye is in a gaseous state, only the dye can move between the overlaid layers without undesirable interlayer effects or movement of other substances between the layers during transfer. A multicolor image is obtained.

Next, the image-receiving layer according to the present invention will be explained. Or white.

The image receiving device is formed from a support and a layer containing polyvalent metal ions. The layer containing polyvalent metal ions provides a metal ion donor containing polyvalent metal ions in the binder. In some cases, the metal ion donating substance itself also serves as a binder. Preferred metal ion donor substances and
-77535, JP-A-55-4821+1, and JP-A-55-129346. As the support used for the receiving layer, those known in the art such as paper, plastic film, plastic-paper composite material phase, etc. can be used. It is also possible to knead polyvalent gold ions into a support and immerse paper, etc. in a polyvalent metal ion solution to produce a sheet containing polyvalent gold ions.) do.

Most effectively, the polyvalent gold ion in the present invention reacts quickly with the released dye (2, forming a desired, parallel-phase complex [2, strongly coordinates with the ligand [~, receiving 1 dust]). There is substantially no metal ion in the layer.Polymer metal ions having such properties include copper (II'), nickel (11), palladium (11), zinc (11), platinum fII), and Kobal) (II) etc., but particularly preferable copper (
ID and nickel (11).

The image-receiving layer according to the present invention may be stacked on the heat-developable photosensitive material before exposure, or may be stacked on the heat-developable photosensitive material after exposure and before development. materials)
The dye image may be transferred in six layers.It is desirable to separate the dye image from the heat-developable photosensitive material by peeling off the image-receiving layer.

The thermal development method of the present invention for forming a color diffusion transfer image is shown below.

(1) A recording material containing the above-mentioned heat-developable photosensitive material was cut into an appropriate size and subjected to permanent exposure. Light sources for image exposure include sunlight, tungsten lamps, fluorescent lamps,
Light sources such as mercury lamps, halogen lamps (iodine lamps, xenon lamps, etc.), and laser light can be used.

(2) Bring the photosensitive layer of the recording material into contact with the image-receiving layer and
~250°C, good 11. Heat at a temperature of 100-2 ()0°C. Heating time is 5 seconds to 180 seconds, preferably 15
~90 seconds. As the thermal method, conventionally known methods used for heat-developable photosensitive materials can be used. For example, a recording material including a photosensitive layer and an image-receiving layer is heated by
There are methods of heating by contacting with a plate or drum, passing through heated air, high frequency heating, or laser beam.

(3) Next, Uke I3! When the layer is peeled off from the photosensitive layer, the color + [Iiii] image of the four elements chelated by polyvalent gold A'A ions is elevated, and the chelated dye is not chelated. Sublimation: It has the drawback of transferring a sublimable dye, in which the qed 枦I re-sublimates due to heat, and the dye 11.+1 image fades. As expected, the image iHg is viewed. Kirani form hν pregnancy r1
Since the dye is a chelate dye, it is stable against heat, light, moisture, etc. 2.) () It has particularly excellent light resistance.

Ministry, in the present invention, to form a multicolored color 11jl+ 1 bed rΣ2) As mentioned above, Z1 which releases dyes capable of forming 1 bite of yellow, magenta, and Noan pattern on the support, respectively. Corresponding to the dye donor η and its wear 1. (sensitized/sensitized film consisting of three different layers, including silver oxide, and other 80% materials) - Exposure, heat development, and heat transfer as described above - 4 -Achieved by

υ) ゛ Shows specific examples of sublimable dyes and color-providing substances that can be chelated. -(4-methoxy/-1-pyridylazo)-2naph[・-le Dye-(3) 2-(2-hydroxyphenylazo)=4-methoxy-1-naphthol Dye-(4) 2-(2- Hydroxophenylazo) = 4-methoxyphenol Dye-(c,) 8-(2-Hydroxyphenylasoone-quinoline 1)ye-(6) 2-(2--Hyl-'oxyfuconinyluane' )-1,4-dimethoxy-phenol Dye-(7) 1-(2-pyridylazo)-2~
Nanotol Dye-(8) 2-(2pyridylazo)-1
-Naphthol-4-nodquine 5-nitrophenol Dye (1
0) 2-13-chloro-2-bili/9ano]-4
-Chlorphenol Dye-Yan 2-(4-hydroxy-2-hyrine,
Ireazo)-4-methoxyphene, /-le Dye-<12) 2 (4-Human Dye-/-2-
Pyridylazo)-4-methoxy 1-naphthol Exemplary dye 111 Kotobuki Trade cpni (1,) cIr3 cpm-(5) CIIs cpCll5c 9 pieces, one-shot list of countries implementing the method for forming strokes invented by Ig do.

夷り和例-1 1-Hydro-? /Ben'Citrian'・-ruji17.
At 26.9, Suiyusha Kosu Vinyl Butyral 25% water bath solution (
,? , 9 Water Chemical Co., Ltd., Esresoku W-201) 24
cc, 7k 116cc.

J: 9/-Lua 0 cc was added and a lumina ball mill was added to obtain a powder 6'1/fraction L7 and a Kushibana dispersion.

1525cc of this wholesale dispersion contains phthalic acid 0.21.9.
Phthalazine" 6jJ, AiIfic Koiro Ichikawa Yomono'
ICPM-'10.89 g1 or less', image agent (1,42
7i, and water-soluble polyvinyl butyral 25% water bath * 5 cc, water 10 cc, and average particle size 0.04
I added 36 m9 of μ of iodine emulsion in terms of silver and took a photo!
(For use) It was applied onto a filter paper using a wire bar VC so that the wet film thickness was 55 μm.

developer Step sea urchin, compared to the dried persimmon 71 sample.

30. OO (IcMs exposure was given.

- 10,000, Ipoly - Water containing 15% water-soluble polyvinyl butyral 10% nickel chloride on paper f? lW per square meter of polyvinyl Bug Ral 75C1 + 40g
A small cloth was added to Totoyo 5 to make an image-receiving paper containing dichloride.

The coated surface of the exposed sample was attached to the coated surface of the image-receiving paper, and after being pressed and heated for a few seconds with an iron having a surface temperature of 150° C., the sample and the image-receiving paper were separated for 7'r-.

Maximum reflection of receiving paper surface K i7 J fil 11.8
5. A negative image of a yellow step wedge with an i4G small reflection density of 0.12 was created.

Example-2 Behe7 Pi! l! 4.59 toluene 2tlcc
, acetone 20cc and polyvinyl butyral 3.2
．． ! i'? r processing, dispersion using an ultrasonic homogenizer.
1 was prepared.

Behen 61? 3. Add 4' and 9 to 4 L'lcc of polyvinyl butyral 8-fold% acetone bath solution in a heating bath.
,, By stirring on ice, dispersion of behenic acid-2
I got it.

On the other hand, phthalic acid 0.20g, phthalazine 0.13g, c
89 g of pm-20 and 255 g of the following developer were mixed into a polyvinyl butyral 8% acetone solution 110 cc K
Solution-1 was obtained by dissolving the solution.

Further, the developer Triflo V vinegar rf2'4 and lithium chloride were reacted in a polyvinylbutycetate 910 wt% acetone solution to obtain Emulsion-1.

dispersion liquid -] to 1 t) cc and minutes ij'i, :fIM-21
Mix 0 cc and add 0.
0.3 cc of 0.5 weight 47i% methanol solution and 20 Da of acetic acid*1.2 mercury were added.

Finally, Solution 1 was added to the sensitizing dye and coated on a transparent polyester film with a wire bar so that the wet film 1'X had a thickness of 74 μm, forming a photosensitive layer.

On top of that, a white reflective layer and an image receiving layer with the following composition are provided, and the receiving layer (
Another transparent polyester film was glued on top of the '177m.

<White reflective layer> (Unit: J/yrt)
Titanium dioxide (average 4Sl diameter 1.5μ) 15 Cellulose diacetate 1.2 Dode/L sulfate 0. (18 ethanol
25 water
30 <Image receiving layer>
(Unit: 1 z/m') Divinegar-thrown cellulose
1.6 disodium chloride/l/
1. (1 ethanol
2I water
42 On the photosensitive layer side of this sample, 17 and 17) lfl L, - 30,
The photosensitive layer was exposed to light at 0 (10 CM·S) and the surface temperature of the photosensitive layer was 1 tl (1'C) for a total of 30 seconds.

The photosensitive layer contains a negative silver image and an unreacted color donor Jfg.
A positive image is formed, and the image receiving layer has a maximum reflection of 41 degrees 1
．． 21. One magenta negative with a minimum reflection of 1 dust of 0.14 was asked.

Example-3 Dispersion-3 was obtained.

4) If/J was prepared with solution-2 having the following composition.

2r) cr: , 15 cc of weld seam-2 was mixed with the above amount 'A't 1tJi -3, average N, child U, O11
Let a certain φIJ emulsion of μ be ip (; 2 + 7, o, z,
y amount was added and coated on photographic baryta paper to form a 5n-photosensitive layer.

Then, instead of 8.71 g of 4-nidroxybenzotriazole <fil> in Solution-3, 7.809 g of 5-nitrobenzotriazole, CPM-C1)
．． 8g Nokawa Ill f/j7 CPM-(2) to 1
1.59 +Ct, c Similarly, dispersion liquid-4 is IF↓.

Take 25 cc of the dispersion liquid 4, add thereto 3.2 cc of a 0.02 wt% methanol bath solution of the sensitizing dye F, and further add 15 cc of solution 2 to form one part of the first photosensitive layer. < wide surface and the second photosensitive layer and L Ir, .

For the sample in which the sensitizing dye was injected, follow the stem wedge and
Sample (A) was exposed to 0,000,000 chas of white light;
) and add λ to the conditions of
'194 was 1-4-1 and was called sample (C) [7].

Separately, a layer of polyvinyl butyral having nickel chloride chips was coated on photographic baryta paper in the same manner as described in Section 1) to prepare an image-receiving paper.

Each sample was exposed to 4'5 light f (S' on the layer side: coated surface of the image paper @1') and heated for 30 seconds with an iron at a surface temperature of 160°C. The ignition and minimum reflection density of the receiver paper of each sample are shown in Table 1 below for each measurement light.

Example-4 (Fixing properties and light resistance) Dye-(2), Dye-(4), Dye-(7)'
E each 5 (1 m 9 & 8% Bolibi, = Rubutilal dissolved in methanol K 10 cc and dried.

Next, in the same manner as in Example 1, the JL obtained in II (1) was coated with a nickel-containing polyvinyl butyral layer and a -4fc polyvinyl butyral layer containing nickel chloride was applied on the receiver paper. , L-described dye (Dye-(2
), Dye-(4), Dye-(7)) were transferred for 1 minute using an iron having a surface temperature of 150°C.

The dyed image-receiving paper obtained in this way was retransferred for 10 minutes with an iron at a surface temperature of 110°C, and the optical density (Do before transfer) by λmax after transfer dyeing and after retransfer (Do before transfer,
D) was measured after FS transfer, and I1~ of r)/11ox100 was taken as the residual rate (10), and shown in Table 2. The city knows that Sadaakiro, who has a high survival rate, is poor.

Similarly, the dyed yarn image-receiving paper obtained by straining was irradiated with a 6,000 W xenon lamp for 4>j ngi (illuminance Vt on the image receiving surface).
60, old) O looks) shi1, before dew L and after carp play)
・Optical density due to λnl a X (before exposure 1) o,
After exposureD) define,l)/l)o X 1(10) candy'! 'r Cooking u ('f'0) Tol-,, as shown in Table 2, A:.

From the result of fLt;, according to the invention, λ-1 is easily calculated! Due to various treatments, the edges of the out-of-stable color curves are white I] [7) It is also shown that the cuffs are IIT white.

Table -1 Table -2 Agent: Kuwa Haya Tsurumiaki (December 22, 2015 U5'1 Commissioner of the Japan Patent Office Kazuo Wakasugi) 1. Indication of the case 1982 Patent Application No. 160698 3 Person making the amendment Relationship with the case Patent applicant address, %ll tl 1 (name (ra,) (127) Konishi Rokushasei Kogyo Co., Ltd. 4, agent 〒105 5, date of amendment order spontaneous 6, number of inventions increased by 1 due to amendment 7. Full text of each item to be amended 8. Details of the amendment on separate sheet.

Full text Masaaki Sode Wholesale 1st Co. 1, Name of Invention Thermal Swimming Color Diffusion Transfer II! Formation Method 2, Claims (1) A thermally non-diffusible color donor and an organic acetate capable of releasing a sublimable dye as a function of development.
! By imagewise exposing a salt-containing heat-developable light-sensitive material and then thermally developing it, an imagewise distribution of sublimable dyes that can be gillated is formed from the color-providing material, and the [A-like distribution] is formed. Slight 4: A part of the spider is thermally transferred to the lower layer containing polyvalent metal ions in the dark development photosensitive material and the polyvalent metal ions in the image receiving layer, and the sublimation 19 that has been converted into polyvalent metal ions and clear 1 is transferred to the image receiving layer. - Forming an image-wise distribution of dye (i- A method for forming a heat-developable color diffusion transfer 1fiI body.

(2) Scope of packed ice, characterized in that the thermally non-diffusible color-providing substance is represented by the following general formula fi+. A color diffusion transfer image forming method.

[wherein, At least one of the adjacent positions of the atom is (a) a nitrogen atom (11 circles Y element atom, acid type atom or IAO atom, t1i 俟 hl this tatsuzohara ryo 1-゛ashi, X) J at least Gt-J represents an aromatic ring consisting of 5 to 7 atoms or a group of atoms that can be completed in a shallow system, and Gt-J
Expressed as ``Kire-1・Residence:'', 8 releases ``Ke1 Hua 11L dye tel) ω as a function of heat development and coats Urukomi 1-''.
] (3) The thermally non-diffusible color-providing substance is represented by the general formula (1) below.
2) A method for forming a thermal development color diffusion transfer layer according to claim 1, characterized in that:

()+1 [wherein, Represents an aryl group.

(4) The IF+tf heat-developable color diffusion transfer image forming method according to claim 2 or 3, wherein A is represented by the following general formula (3)" or (4).

7 [In the formula, J, It2tR+ R11* R5+ R6
+ R7 and R8 are each one of water
It represents an argylsulfonyl group, an arylsulfonyl group, a carbamoyl group, an acylamino group, an alkoxy group, a sulfamoyl group, a sulfamino group, or a hydroxy group.

However, at least one of R1, R2, R3 and rikll(1)9, and R5+ R6* R7 and It
At least one of H is a ballast group that lowers the center of gravity of the thermal diffusion ++.

At least one set of Ill and R2 and RII and at least one set of R5 and R6, R6 and R7, and R7 and R8 are bonded to each other to form a saturated or unsaturated 5- It forms a 6-membered structure and -C is also good.

Jt represents a divalent bonding group, and m represents 1f spanning O. ] (5) Polyvalent gold stripe ions are used in copper (ll), nickel (
tD, support ship (n), platinum (II), palladium (1) ×
is cobalt (It)] J'J+; A method for producing a thermally developed color diffusion transfer image.

”So dry - Margin 3, Detailed Description of the Invention The present invention relates to a method for forming a heat-developable color diffusion transfer 1IliI image. Color ii! The present invention relates to a thermally developable color diffusion transfer image forming method and method capable of obtaining an iI image.

A method of forming a color 1 Buddha using a photosensitive substance (halogen atom) is a method using a dye formed by an oxidized product of mulberry and a 1 color dye. There are known methods such as whitening to obtain rI!JI images (silver dye bleaching method), and color diffusion transfer method in which the dye used in so-called instant η stain is diffused and transferred using alkaline treated gauze. Both methods require a water-soluble processing solution and have the disadvantage that the processing for forming an image is complicated. Therefore, there remains a need to develop a photosensitive thermal development color image forming method that forms a color image using a dry process and a simple process.

As a thermal development color image forming method, Shiroe is published in Tokuko No. 1978-7782, Mokukoku Toki No. 761,200, No. 3.764,328, 441;i;I us 56
iC in No. 27132, Mukai No. 56-27133, etc.
As shown, the omega form of color-forming keratin and cuff 2-
There are methods of forming color images by using these methods, but in these methods, a silver mark is also formed where a dye image is formed, so that the color image is formed in the form of a color image. The white background may become cloudy due to the II image, and the white background may be contaminated due to the 7 lint γ9 on the surface of Sugi 1.1. To eliminate these problems, a fixing step is necessary, which undermines the advantage of thermal imaging, which is a simple processing method.

Other thermal development color image forming methods include, for example, JP-A-52-105821, JP-A-52-105822, and JP-A-52-105821.
6-50328, US Pat. No. 4,235,957, etc., silver dye bleaching method is used. However, due to unbleached discoloration in these methods, 'r
It may be necessary to use an oil-based sheet containing a 5+ acid or silver chloride complex, and the processing may be complicated.
It has drawbacks such as the use of Il'.

E1 inch white yet another heat development color II! As the II image forming method, there is, for example, the dye competitive salting method described in Research Paper 16966, published in May 197 G'. This method is attracting attention as a method to compensate for the shortcomings of the two methods mentioned above, but it is difficult to completely convert the dye into silver salt when synthesizing colored thread silver salt, and the dye becomes silver salt and the dye is removed. This remains, resulting in fog in the image. Furthermore, when transferring the dye, the dye is transferred to a solvent, so not only the dye but also other undesirable additions! Of course, it has the disadvantage that the color becomes muddy due to the transfer.

Therefore, a first object of the present invention is to provide a method for forming a PJA boundary color diffusion transfer image using a thermal non-diffusible color donor compound capable of releasing a sublimable dye having chelating ability by heat: LJl. be.

The second object of the present invention is the color accumulation iI of the form hv! I
To provide a method for forming a thermal mass image color diffusion transfer iIL+1 image in which the I image is stable against environmental conditions such as heat, light and humidity;
It is an object of the present invention to produce a thermally non-diffusible colorant that can produce a sublimable dye similar to that of gyrate as a function of temperature.
A heat-developable photosensitive phase material containing an organic silver salt and a heat-developable photosensitive phase material is then chelated by irradiation, hot oil, and imaging.
An image-wise distribution of a sublimable dye with a sublimable color is formed from a color-providing substance, and at least a part of the image-wise distribution is transferred to a heat-developable photosensitive material and a layer (containing a related polyvalent gold kA ion). This is achieved by thermal transfer and forming an IM wax distribution of sublimable dye chelated with multivalent all-set ions in the receiver layer.

``Ascending rod'' generally refers to ``the property of changing from a solid state to a gas without changing the entire body state,'' and there are many dyes known in the industry that have this ascending property. (Gtai 1ilj is listed in the ``Some 1 Handbook'' (marumono).) +#Sublimable dye 1! (In a vortex, it is a solid with ll-n motion, and if there is no solvent, 7L is non-diffusive. If the force, heat, and temperature exceeds Ichihion's law, it will sublime and become a gas, and it will be diffusive. For example, a sublimable dye coated on a support is heated, vaporizes it, jumps and diffuses from the support. (Image received) If the sky is tl i'l-,
Even if the dye is not attached to the support, it is adsorbed and deposited on the surface or inside of the image-receiving layer, forming a dye image. Sublimable dyes also have the ability to diffuse between layers in a gaseous state. That is, even if there is an intermediate layer between the sublimable dye layer and the receiver layer, the dye can be diffused and transferred without using a solvent.

Therefore, by using this timing, it is easy to design a multi-layer color thermal dust image lightning material.

The formed dye image is a non-sublimable dye because it is chelated, and does not have the internal discoloration that is a drawback when using a sublimable dye. If you follow the method of misfire Iυj, you can generate a rectangular image just by processing with heat, and color II! ++ Buddha can be obtained.

Because it is produced using the diffusion transposition method, it does not require desilvering, and since the 1iii II image produced by JS is a chelated dye image, it is free from heat, light, moisture, etc. It is a dye image that is stable against environmental conditions and has particularly excellent light fastness.

The chelatable sublimation 4g1 dye in "Non-explosion" has a sublimation temperature of 50 to 250°C, more preferably 50 to 1
70C, which is capable of forming a chelate complex with at least two coordinations with a polygonal metal kJi ion, and more preferably has a sublimation temperature of 50 to 1
It is an azo dye that can form a tridentate chelate complex at 70°C.

In strong alkaline liquid that is harmful to the human body, [jl, element diffuses 1-
7teiI! Compared to the conventional so-called instant copying method, which forms a 11-inch image, the heat-developable color diffusion transfer method of the present invention involves heating the transferred image at a certain temperature for a certain period of time, thereby reducing safety and other disadvantages. It's a bad idea.

1. During the FlX thermal imaging phase) lj b'y or V
In the conventional method of transferring with something like a hot solvent (thermal solvent),
Although C is difficult to implement in a multilayer system, it is easily possible using this method.

In the present invention, the color donor material is thermally non-diffusive and substantially does not cause intralayer or interlayer diffusion even when heated. In the present invention, the color donor (b) is capable of releasing an oxidizing dye precursor as a function of development, that is, as a result of heat development, and is capable of releasing an oxidation-reduction reaction that occurs in the process. The release reaction occurs either directly or indirectly through cross-oxidizing agents and the like. J′L, which is released by heat development reaction, is a low-molecular-weight sublimation dye or glecaser,
Since the dipole moment is small and the hydrophobicity is high, the interaction with the hydrophilic binder is small.
It spreads easily without requiring 6jiIJ. Therefore, in the present invention, the combination of a sublimable dye or a sublimable dye precursor and a hydrophilic binder is effective against diffusion and transfer, ie, the sublimable dye or sublimable f! ! Preferably, the color donor material, which is capable of producing a grayscaler, is added to a hydrophilic binder. In this way, when a hydrophilic binder is used, the color-providing substance is non-diffusible (for example, λ has a ballast group and/or a hydrophilic group) to make it non-sublimable in the binder. A hydrophobic binder may be cooled in the hydrophilic binder to the extent that it does not interfere with the non-diffusibility of the color-providing substance and does not interfere with the diffusivity of the dye or dye precursor. It is also g1 to do
Noh demeru.

In contrast, the sublimable dyes released by the sublimable dyes and the sublimable dyes include decomposition, elimination, and starch exchange reactions, but in the present invention, the 14F point It is effective to use a 1β converting coupler, a γ-zo coupling method, or an oxidizing power ruffling method.

Example λ is aroma b5. - Noboru 1η strain is a dye formed by a 7 azokatuf ring or a t-oxidation coupling with a kafurer that has a ballast group through a bond at the active site, such as the hexamer of the 1-class amine coloring machine. It is a lifting platform that has an aromatic-grade amine, a derivative of the active substance, and a bond to the active site to produce a sublimable dye or sublimable dye recursor. In the cyazo-cutoff ring or oxidized cut-off link with caffler as a leaving group, the ascending dye or Jf4.imageable dye is released.

The method of the present invention provides a non-nuclear dye capable of releasing the chelatable enzymatic dye of the present invention;
It is called a septic color-donating substance (hereinafter referred to as υ, simply U color-donating substance) GA-1. ) is a compound represented by the following general formula (II).

represents an aromatic ring having the general formula (1, I, X represents an aromatic ring in which at least one ring is composed of atoms of 5 to 71M11) or a small group that requires the formation of all the atoms; and at least one of the adjacent positions of the carbon atom bonded to the azo bond is (a) a nitrogen atom, or (b) the nitrogen atom, the atom atom 5! is a carbon atom substituted with a sulfur atom, and is suitable for monkey ten. It may be substituted with a bamboo substituent, and preferred substituents include an alkyl group,
γ-alkoxy&, '/j'/ group, hydroxyl group, thiol group, thioalkoxy group, or haloken group.

At least one song is composed of 5 to 7 atoms. Change Wl” with a suitable editor!
Examples of unpleasant compounds include benzene salts, naphthalene rings, biline salts, and quinoline salts.
Preferably, the m group is an alkyl group, an alkoxy group, or a γ)
A group, a hydroxyl group, an amino ring, or a halogen group.

G stands for chelate 1F7 group, and is preferable) "Hydrothermal Mut
;, amine group, methoxy group, thiol group, thioalkoxy group, etc.).

8. Lid as a function of heat development
Represents a group that can be illuminated.

Another desirable color donor! Iy1 + trade as j' king n1
There is a compound J represented by the general formula (2).

(31 (in the formula, represents a γ cetyl group, a benzol group, a cyano group, or an acetamide '11.., and 2
represents an argyl group (preferably a methyl group) or an aryl group (preferably a phenyl group).

In the general formulas +11 and (2), the group represented by the following general formula (3) or (4) is a group that can extrude a photochromic dye site as a function of heat development to generate A″c′. be.

c7 In the formula, R1,lζ2+1ζ3, ltg, R5,tζ
6. R7 and R8 are each a hydrogen atom, a roken atom (preferably a chlorine atom, a bromine atom, an iodine atom),
Alkyl group (preferably an alkyl group having 1 to 24 carbon atoms, such as methyl group, ethyl group, t-butyl group, S-octyl group, pentadecyl group, cyclohegycyl group, trifluoromethyl group, benzyl M % phenenal group), aryl group (e.g. t:r phenyl group, naphthyl group,
tolyl group, medinal group, etc.), acyl group (for example, acetyl group, tetratechanoyl group, pivaloyl group, benzoyl group, etc.), γrugyloxycarbonyl group (for example, methoxycarbonyl group, benzyloxycarbonyl Mfx, etc.), γ-aryloxycarbonyl group (Sec. 11
p-phenylsulfonyl group, p-MJruoxycarbonyl group, α-f71-xyJJrubonyl group, etc.), alkylsulfonyl group (methylsulfonyl 2M
nido), 71J-rusulponyl M (e.g. phenylsulfonyl group, etc.), carbamoyl group (e.g. menalcarpamoyl group, butylcarbamoyl group, tetradecylcarbamoyl group, N-methyl-N-dodecylcarbamoyl group) group, phenylcarbamoyl group), acylamino group (
11-butylamide group, β-phenoxyenalamide group, phenoxyamide group, β-methaneX sulfonamide enalamide group, β-methoxyenalamide group, etc.), alkoxy group (preferably 1 carbon atom number) (18 gamma alkoxy groups, such as oxmethoxy group, ethoxy group,
octadecyloxy group), sulfamoyl! (example,
t represents a methylsulfamoyl group, phenylsulfamoyl group, etc.), a sulfamino group (eg, methylsulfamino, tolylsulfamino), or a hydroxy group.

However, it is preferable that at least one of R1, R2, R5 and (1) and at least one of R5, R6, R7 and R8 be added, and a ballast group that reduces thermal diffusivity, such as a sulfo group, It has a group containing a hydrophilic group such as a carboxy group or a hydroxy group, or a group containing an alkyl group and having eight or more carbon atoms on each side.

Also, 1, at least one set of 1 and R2 and R3 and RIl, and at least one set of R5 and R6, R6 and R7 #j: Lli is bonded to saturated 1 or unsaturated 2 A divalent bonding group represented by 1-2, preferably 11 (where L represents an oxygen atom or an 117 atom), and Ill represents 0 or 1, When m is O, the group represented by the general formula (3) is directly bonded to the photochromic dye residue it.

The group C” represented by the above general formula (3) “conventional/!” (J) 1 □ 1 replaces the active point of the naphthol or phenol type cyan coupler on the given page, and the cyan coupler can include any cyan coupler known in the art. can.

Next, the heat therapy combined sensation photophrase 1 of the present invention will be explained.

As a heat-developable photosensitive material, conventional black and white i#1
As a thing that forms an image, for example, "O"
4-Q, No. 43-19166, No. 46-4728,
44-2ti532, 45-127 (October,
Same No. 15-18416, Infringement Unexamined Patent Publication #fi49 526
26 months, etc. are written: I L te LQ , Z) j ')
('(% support, jΔ elementality... Rokenization, organicization 8
'! + 3 phantom 4 (silver) (3-pronged Q: transfusion, development le
and bar [tan-chi] and et al (1-bed J 戎Sa)'; 4-valve, and clearly L, the above-mentioned known heat-developable photoreceptor can be used. .

IA development photosensitive materials further include color toning agents, chemical sensitizers,
Development N1. ! 1, antifoggants, spectral sensitizers, filter dyes, antihalation dyes, etc. may be added.

Substances constituting the above-mentioned heat-developable photosensitive material - support, photosensitive silver halide, gold M (silver) salt or complex of organic compound, binder, binder, toning agent, chemical sensitizer, development adjustment remover,
Anti-fogging agents, spectral sensitizers, filter dyes, antihalation dyes, etc. were published in June 1978, and detailed information was published on pages 9 to 15 of Zana Disclosure Magazine. JL et al. can also be used for the composition of the thermal dust image photosensitive material used in the present invention.

For example, binders that can be used in the present invention include gelatin, gelatin derivatives, casein, sodium caseinate, canned white products such as albumin, cellulose TDT conductors such as ethyl cellulose, polysaccharides such as 7-kistran, Kannu, and Arabica. Natural substances such as rubber, rubber tragacanth, and latex-like vinyl compounds that increase the dimension stability of photographic materials and synthetic polymers such as those described below are included.

For example, U.S. Patent Nos. 3.144586, 3.19 &
No. 386, No. 3.064674-1 No. 3.220
．． No. 844, No. 3,287.289, No. 3,41
1.911, each specification VC is disclosed. Specific examples of polymers include tJl alkyl acrylate, methacrylate-1, acrylic acid, sulfoalkyl acrylate, etc. 1. A water-insoluble polymer made of methacrylate yarn. -1: tc1 polyvinyl butyral, polyacrylamide, cellulose acetate phthylate, cellulose acetate flobionate, polymethyl methacrylate, polyvinyl pyrrolidone,
follisnarene, ethyl cellulose, polyvinylpyrrolidone polyimbutylene, phthalene copolymer,
Vinyl chloride-vinyl acetate copolymer, vinyl acetate-vinyl chloride-malley f:/copolymer with acid, polyvinyl alcohol, polyvinyl acetate,
Pencil cellulose, cellulose acetate, cellulose globionate, cellulose acetate phthalate fxt
1tS'! , le.

A specific example of the low heat-sensitive material used in the present invention will be explained.

The heat-developable photosensitive material according to the invention consists of at least one layer (A) provided on a support. The layer contains (a) a photosensitive silver halide, (b) a silver salt of an organic compound, (C) a highly taxed material such as a developing agent, and (d) a color donor Q; y + trade of the present invention in a binder. (component value),
(b).

(C) and (d) may be contained in the same layer, respectively, as long as they are in a state where they can react with each other, or may be contained in separate layers, and the absorption wavelength of the color-providing substance but,
If the wavelength region overlaps the sensitivity of the light-sensitive silver halide with which it is combined, the color-donor is applied to the light-sensitive silver halide layer at a position that does not reduce the sensitivity of the light-sensitive silver halide with which it is combined. It is preferable that it is contained in Jij located on the opposite side of the direction.

However, the absorption wavelength of the color (I) is different from the absorption length of the dye generated in the image-receiving layer, and the photosensitive range of the photosensitive silver halide combined with it is different from the absorption wavelength of the color (I). If not, use the same color donor and photosensitive halogen.
It is also possible to feed pigeons with awns.

In a preferred embodiment of the invention J1~) bowl image sensitizer 4!1'4'+&', -Frit' on the support, 4 layers from 3 different layers (with -C Immediately, C+, image-receiving layer
! .

- A giant that emits ljK pigment (JL humiliation trade and 10゛)
1. The corresponding spectrally sensitive silver halide stones a-b are composed of three different layers (layers (A) and L).
・It's a gaseous state
C: At a certain 7th grade, only the dye could move between J+/c- and J9, excluding the transfer).
) 1 undesirable Yonoso young fruit or other substances 4.6 multicolored without accompanying sea bream if! ! 7 images are obtained.

"1" margin Next, the image receiving layer according to the present invention will be explained.

The image-receiving layer t according to the present invention contains polyvalent metal ions in the image-receiving layer or on the oligodegradable layer, and has a substantially colorless or slightly white surface.

The image receiving layer is formed from a support and a layer containing polyvalent metal ions. The layer containing polyvalent metal ions may contain a metal ion donating substance containing polynodal metal ions in a binder, or may contain only polyvalent metal ions. The metal ion donor may itself act as a binder. As a preferable metal ion donor substance, Japanese Patent Publication No. 36-775
No. 35, JP-A No. 1ii 455-48210, JP-A No. 55-1
There is one described in No. 29346. As the support used for the image-receiving layer, those known in the art such as plastic film, plastic film, and composite materials are used.In addition, metal ions may be kneaded into the support. Alternatively, an image-receiving sheet containing multiple metal ions can also be obtained by immersing paper or the like in a polyvalent metal ion bath.

In the present invention, the most effective polyvalent metal ion is the one that quickly recoils from the released dye, forms an S (solid body) with the desired hue, strongly coordinates with the ligand, and is image-receiving. Real in I9
Orally it is colorless. Such a polyvalent metal ion with +'1 and 1-! , jjll (II), nickel (0), para/9m (118, support vessel (10), platinum (
11) and cobalt (It), but particularly preferred are copper (U) and nickel (Y).

In fact, the image-receiving layer for brightness may be in a stacked relationship with the hot dust-drinking photosensitive material, or may be stacked on the hot dust-drinking photosensitive material before development. Good, see you again 3
The giant tree image may be transferred by stacking the JQ image temporary image receiving layer on top of the hot dust layer. After the transfer, you can use a low 1D original through the support without worrying about removing the insurance, but be sure to peel off the image-receiving layer. It's like 8J.

Lower margin Present invention C] An example of a method for forming a heat-developable color diffusion transfer image is 4 scraps below 9.

(1) The above-mentioned limitations 1) After cutting a recording material made of a photosensitive material, or a photosensitive phase material and a receiving layer (or an image receiving sheet) into a suitable size, an image is produced. Expose.

Light sources for image exposure include sunlight, tungsten lamps,
Light sources such as fluorescent lamps, mercury lamps, halogen lamps (such as iodine lamps and xenon lamps), and laser light can be used.

(2) About 50 to 250 C, preferably 100 to 2
Heat at a temperature of +10 C. When heating, listen for 5 seconds to 18 seconds.
0 seconds, and 15 to 90 seconds when the case is closed. As a heating method, conventionally known methods used in heat development photosensitive moon phase can be used, but for example, λ is about 1 prefecture. Touch the recording material, including the foil and image-receiving layer, to a heated sheet or drum! - alternatively, passing through heated nitrogen gas or heating with a laser beam.

By peeling off the image-receiving layer from the photosensitive resin, chelate (L
: - A color image created by the dye is iii et al. 8 This cleared dye P is sublimated (in this case, 7% of the dye is re-sublimated by heat) However, one disadvantage of transferring a dye that can be transferred is that the dye fades, and both images are fixed in place. ,
It is resistant to light and moisture, and has particularly good light resistance.

A.2 Invention: 1. Forming a multicolor image H
) Runike iji + As mentioned above, the color donor that releases the dye capable of forming a dye image corresponds to '+v* and that/dere. A small amount of silver halide and other thermal dust particles containing spectrophotometrically deposited silver halide and other thermal dust particles (a layer consisting of at least three hearts) is exposed to light and heated in the same manner as described above. Low, achieved by thermal transfer in a stacked relationship with the receptor layer. to lead.

[Dye attached to example No. 4] D y e -1ll 2- (4-methoxy-2-
Bilysylazo)phenol D y e -1211-(4-methoxy-pyridylazo)-2-naphthol 1) y e -4312-(2-hydroxyphenylazo)-4-methoxy-1-su7thol D y e -1412 -(2-hydroxyphenylazo)-4-methoxy-7enol[)ye-+518-(2-hydroxyphenylazo)
-Quinoline Dye -(612-(2-hydroxyphenylazo)-1,4-cymethoxyphenol Dye-(7) 1-(2-pyridylazo)-2-su71·-le Dye -1872-(2 -pyridylazo)-1-su7
Thor Dye-(912-(3-methoxy-2-pyridylazo)-4-methoxy-5-nitrophenol Dye-2-(3-chloro-2-pyridylazo)-
4-Chlorphenol 27-Dye-(11) 2-(4-hydroxy-2-bilinluazo)-4-meloxyphenol Dye-(12) 2-(4-cdrogycy-2-pyridylazo)-4-methoxy -1-Naphthol [Exemplary color-providing substance] CP M -Ill c P M -t5) Ct13 Hereinafter, the method of forming an image using the present invention will be described with reference to IJ.

Example-1 To 7.26 g of 4-human mixy benzotriazole m, 116 cc of water and 70 cc of methanol were added to 24 aqueous solution of water-bathable polyvinyl butyral 25 (T*Mizu Kagaku Co., Ltd., Eslec W-2OX), and the mixture was heated in an alumina hole mill. Grind and disperse to obtain a silver salt dispersion.

? -CD 1. ! To the salinity number RFF 125cc, add 0.21 gs of 7 tal, 0.16 g of phthalazine, 5 g of the light blue donor material CP M-(1) o, 89 g, and T' development.
55g, and water bathed polyvinyl bunral 25% water soluble 6scx, water 1ocr,'g et al. average particle size 0.04
The emulsified silver gelatin of μ was replaced with silver and 36 μm was added, and the wet film thickness was 55 μm on baryta paper for viewing angles. Oi 17 with a wire bar so that u is formed.

30. Pass the dried sample through a step wedge. OOOCMS (2) exposures were given.

- 10,000, IPOLY - A water bath solution containing 15% water-soluble polyvinyl butyral and 100% nickel chloride was applied on paper so that the amount of polyvinyl butyral was 1.40 g per square meter. made.

Closely contact the coated surface of the OfJ recorded sample with the tin cloth blood of the IIL recording paper, heat it with an iron at a temperature of 1500 for 30 seconds), and then peel off the sample and the receiving paper. did.

CT &j: A negative image of a yellow Stellar Two Wedge with a maximum reflection density of 0.78 and a minimum anti-reflectivity of 0.19 was obtained.

Example-2 4.5 g of behen him, 20 cc of alcohol, 5 ml of water
α, water-soluble polyvinyl butyral 25 water-soluble M15
Add cCf and disperse with @B wave homogenizer - [1]
was prepared.

10,000, phthalic acid (+, 20 gz 7 tagine 0.1
3g.

hIJ exemplified color donor substance CPM-t 210.89 g and the following 3jl Migashi 1.55 g were dispersed in a 24 hour curved ball mill with 65 liquid 4 (1:1) of polyvinyl butyral 8-water monoalcohol (1:1). lu solution-[1] was obtained.

L dust image removed) CH In addition, milk was removed by reacting 1 inch of truffle 0-mouth acetic acid and lina bromide in a polyvinyl butyral xo4qsγ settone solution.
r: Got it.

0080 minutes 11 sentences - [:l:) 1,0 匡ni - F6 self J
(0.3CC due to 1.05W% methanol bath)
1 and r”1. Added Master and Disciple 2 Water Lie 20η Purple.

[Kosokan pigment]

-ft, solution-[1] was added and coated onto a transparent polyester film with a wire bar to a wet film thickness of 74μ to form a photosensitive layer.

Above that, below, IJ! A white reflective layer and an image receiving layer were provided, and another transparent polyester film was adhered onto the image receiving layer.

<White reflective layer> (Unit: g/+ν?)
Titanium dioxide (average particle size 1.5 μ) 15 Cellulose diacetate 1.2 Dodecyl (&+C6%
! Sodium 0.08 ethanol
25 water
3゜〈Image receiving layer〉
(Unit: g/F7/)Cellulose diacetate
1.6 nickel chloride
1.0 Ethanol 21 Water 42 Sensitivity of this sample 4! The + layer side was exposed to 30,000 CMS through a step wedge, and the photosensitive layer side was exposed with an iron at a surface temperature of 10° C. for 30 seconds.

A negative silver image and a positive image of a ten-reactive color-providing substance are formed on the photosensitive layer, and the image-receiving layer has a maximum reflection grain size of 1.0.
6. A magenta negative image with a minimum reflection gravel level of 1.17 was obtained.

Example ~ 3 The above composition was dispersed in a lumina ball mill to obtain a
! L solution-[3] was obtained.

A solution [2] having the following composition was prepared for each town.

Doossein gelatin 1. oltJrt related aqueous solution Seed aqueous solution ladle! + ii self-dispersion 'IW-(3]2 5 Ce and
After mixing 4 series rp', i, - [2':l 1 5cJ:, add 11g of C11, calculated by adding 11g of silver emulsion with an average grain size of 0.04μ, for photography) (Layer 1:3'ζ0 on lighter paper and the 4-hydroxybenzotriazole silver 8.
For 71g of puno, 5-nitrobenzotriazole 7
．． 80g% M-il
CP M −(2
Dispersion liquid-[4] was made into 111.5g in the same way as a:i i
c.

Mark 25 on the dispersion side - [4], and mark - +1 of the FB self-sensitizing dye. (12+3413-(96 Meknol bathtub: 2 squares, 11 units, 8 Rani feiill C2
] (L-15C1: 1Lje-CXhi - A second photosensitive layer hJ*, 1I: L-1.

[Ha...j〆Giant rope]

1:3F (6S03C
5116Sfl U111! i cr 7 Ifr trial phase (7), trace the 7 Ifr test phase and give 100,000 CMS white light. l &(-additionally Kotanokushisoten filter j
The one using the value 74 is a complimentary copy ((Bu,
In addition to sample conditions, Kotatsukuratuten Filter Ugly 94
The ligature was used as the sample.

-Real bI on fuheri tadayo baraita paper! ,! A nickel chloride-containing polyvinyl butyral layer was coated using the same bj7 method as described in Shin J-1 to prepare a 1:r paper.

Align the receiving wave n (O cloth ■ on the M'X optical layer side of Nago 1,
Surface dr+warm] Pressure was applied for 30 minutes using a 60 C iron. The tl of each sample was ground (J
:Aat's maximum 4-ch-' AU small repulsion sensitivity is measured as shown in Table-1 below. , Dye-(4)
, Dye - (7-11) 1゜50■8
%Polyviny A7''Jral methanol i''; rα
Dissolve 1L in 10cc and apply a wet film thickness of 55μ on polynisdel film.
Drying 1. -'y'r,.

Then ν, -h! ! 1. In the same manner as in 11-1, apply a nickel A. 68 Cloth ni uke can (on paper, ``-:'
w to U, + e floor CD y e -(2) ', Dye
-(41,Dye-(7))Kl 50r:(1)ge
mlL.

It was transferred for 1 minute and 101 minutes with an L-temperature iron.

This °,t,-rii! ``Ranoshifc'j (1) >7'i 2nd image y: 6-tio Re-roll for 10 minutes with an iron with a surface temperature of 0℃, immediately after the transfer bundle is attached, and by λ1118X of 141 transfer. The optical filtration L (DO1 circle transfer f!, D before retransfer) was measured, and the value of D/DQ 1 mountain with a large survival rate > 11 hearts (・'1- is good, i< then (-)z, 011"J+, 'R and 1!tkLl'
j 71-f%' 1134 +14(611 ('
) fl W xenon lamp for 48 hours 11α (image receiving surface 4.1
(L looks) and press the button V1 in front of the red cover and λ11
Optical density by 1aX (1. Original image I) 0. Jealous D)
Measure 1)/T3o x 100 and leave the value 1)/T3o x 100.
Let n=(&) and show in Table-2 1. *.

This Jl et al. The color is also HI
Mt'de/) Kotokawa〃4ru.

6-1 (.

One, 1. □ 546nn, 4□1□4゜E9.1 one table
-2 T+F Patent Application Applicant - J-46 Shakaku Kuri Co., Ltd. Procedural Amendment (Spontaneous) January 25, 1980 Patent Office Kisugi I 11 Daiden 1, Display of Case 1988 Waiting) Application No. 160698 2.
1 White 111's name 2.j- Relationship with the incident -: r ri'l prominent person 4.
Person "r" 1056, Number of inventions increased by amendment Contents of amendment 1 430 members of CPR (6) in the specification 1'1
j Add the following after Hiro-style.

Record -IYwasu.

Claims (1)

[Scope of Claims] (1) f51 (non-diffusible color-providing substance is...
-Yotoyo. After imagewise exposure of the photosensitive material, thermal development is performed to form an imagewise distribution of the gyrate dye from the combined lFj substance, and at least -
81~ are thermally transferred to an image receiving layer containing polyvalent metal ions in a stacked relationship with the heat-developable photosensitive material, and winter value metal and metal ions are added to the receiving layer 11. 14. Forming an image-wise distribution of dyes. ) A method for forming a thermal dust image color diffusion transfer image 13, characterized in that: (2) Thermal non-diffusive color donor ILr↓ is represented by the general formula (1) in F
A heat development one-bed color diffusion transfer image forming method, characterized in that: General formula (1) [In the formula, XI represents an atomic group that can be safely formed into an aromatic group in which at least one salt is composed of 5 to 7 atoms; , and 1 bonded to the azo bond
,? At least one of the adjacent positions of the ≠19 atoms is (a) a nitrogen atom or (b) a carbon atom surrounded by a nitrogen atom, an oxygen atom, or a sulfur atom, and X2 has at least one ring. From 5 to 7 19 children, the necessary atomic groups are represented in (σ constituting the aromatic ring or ip complex formed by q).
G frt represents a chelating group, 11 releases a subsaturated dye moiety upon thermal development; 1. Represents a glutinous group. ] (3) Claim No. 11 (11) Thermal development color enlargement transfer image forming described by J.D. Method. Z2 represents a `r-alkyl group or a V,t-aryl group. ] (4) Is A the following general formula (3)? , 1' + 4
t+ii of the patent claim, which is characterized by the + symbol
The method for forming a heat-developable color diffusion transfer image according to item (2), item (1) or item (3), item (2). General formula (2) ) General formula (3) OI] 7 (wherein, RI + R2v R4* R4+ R5+
R6+R? and R8 are each a hydrogen atom, a rogen atom, an alkyl group, an aryl group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group,
It represents an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, an acylamide group, an alkoxy group, a sulfamoyl group, and a nulphamino group. At least one of Tashi7, R1, R2, R3, l- and R4 and R5r '6 r R? and R, (7
At least 1-tl- of 1 is thermally diffused +1. +1
゛, it is the final group. At least one of R4 and R9 and R3 and R4, R3 and Rs, R,,! : R7 and U
At least one pair of R7/l-R2O is bonded to each other,
2, saturated, tII and Q, 1 unsaturated oro 5-6#uj
L forming H? Good too. J&:t represents a divalent bonding group, m represents 0 and 1,) (5) Multiple times? )%'r ion is r: Tsukasa (II)
, :Ninokel (IT), ][/d(II), Platinum (If
), Palladium CH)